Silica Aerogel Composites With Embedded Fibres

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Materials Chemistry A
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Silica aerogel composites with embedded fibres:

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Cite this: J. Mater. Chem. A, 2019, 7,

a review on their preparation, properties and
22768 applications
ab b *a
Teresa Linhares, Maria T. Pessoa de Amorim and Luisa Durães
Silica aerogels are among the lightest weight solid materials and exhibit other unique properties, in particular an
outstanding insulation performance. However, these nanostructured highly porous materials show inherent
brittleness that makes their processing and handling difficult and constrains their use in common daily
applications. One of the most convincing and effective strategies to reinforce the silica aerogel structure is
the manufacturing of aerogel composites with embedded fibres, which significantly contributes to widening
their applications. This review encompasses a complete survey on scientific achievements related to silica
aerogel composites reinforced with all types of fibres (natural, man-made, organic, inorganic and
nanofibres), describing their synthesis approaches and properties. The influence of the embedment of
different fibres on the final properties of the composites is thoroughly reported, considering their amount in
Received 8th May 2019
Accepted 19th September 2019
the matrix and/or their specific characteristics, namely morphology, orientation and optical features. The
applications linked to the fibre-reinforced silica aerogel composites are briefly addressed as well, evincing
DOI: 10.1039/c9ta04811a
developments in typical functions of aerogels, as thermal and/or acoustic insulators and adsorbents, and also
rsc.li/materials-a in emerging uses, for example as sensors or technical and protective apparel.
drawbacks, such as dust release,22,34,35 hydrophilicity,9,33,35 volu-

1 Introduction metric shrinkage,30,36,37 time for processing,38–41 and ultimately, the
The aerogel was deemed as the ‘miracle material for the 21st prohibitive cost of silica aerogels9,34,42,43 (8–20 fold more costly
century’1 due to its highly porous structure, having a network of than polyurethane foams),5 need to be overcome, in order to
connected particles resembling a pearl necklace, with an air broaden the applicability of such auspicious materials.
volume of 80–99.8%.2 This unique layout imparts to aerogels Strategies for reinforcement of silica aerogels are an efferves-
the status of the lightest solid materials with the best insulation cent topic of scientic research, either through the use of appro-
properties.3–7 Other important attributes of this new-generation priate additives or by ne-tuning the synthesis conditions.44,45 The
material are its high specic surface area (100–1600 m2 g1) and manufacturing of silica aerogel composites with embedded bres
a very low refractive index (1.007–1.240).2,8 is one of the most effective techniques to widen their applica-
Adsorbents of harmful compounds,9,10 sensors,11 dielectric tions.37,46–48 However, in terms of scientic reviews, there is a small
materials,12 ltering media,13 Cherenkov detectors,14 kinetic number of publications on this topic, and generally each review
energy absorbers,15 substrate for catalysts,16 carriers,17 extract- covers a specic type of bre or nanobre.49–53
ing agents,18,19 protective clothing,20 and even art sculptures21 This work intends to highlight the achievements of scientic
are among the reported end-uses of silica aerogels. Undoubt- research on silica-aerogel matrices with all types of bres, pre-
edly, thermal and acoustic insulation are the most signicant senting their properties and discussing strategies to encourage
applications of silica aerogels,22,23 with profuse and detailed their common daily applications. The effect on aerogel
published studies.24–29 composite properties of some parameters related to the bres
In spite of the unique properties provided by the nanoscale (morphology, orientation, amount, and thermal resistance) is
porosity, the use of silica aerogels in common daily applications analysed. The applications linked to the bre-reinforced aerogel
has been constrained, mainly due to their inherent brittleness composites are also briey addressed.
that makes processing and handling difficult.30–33 Other intrinsic
a
2 Brief description of silica aerogels:
CIEPQPF, Department of Chemical Engineering, University of Coimbra, 3030-790
Coimbra, Portugal. E-mail: luisa@eq.uc.pt; Fax: +351 239798703; Tel: +351 synthesis and properties
239798737
b
2C2T, Center of Science and Textile Technology of the University of Minho, Campus de Silica aerogels are synthesised through sol–gel chemistry,
Azurém, 4800-058 Guimarães, Portugal dened by IUPAC54 as the “Process through which a network is
22768 | J. Mater. Chem. A, 2019, 7, 22768–22802 This journal is © The Royal Society of Chemistry 2019
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Review Journal of Materials Chemistry A
formed from solution by a progressive change of liquid

precursor(s) into a sol, to a gel, and in most cases nally to a dry
network”. The precursors can be either inorganic metal salts or
metal alkoxides, but the relatively easy chemistry and versatility Scheme 1 Chemical reactions in the sol–gel process of alkoxysilanes.
of silicon alkoxides make them the most used precursors in sol–
gel chemistry of silica,55 for example tetramethyl orthosilicate
(TMOS) or tetraethyl orthosilicate (TEOS). TMOS is more reac-
a polymer-like gel, made from chains with few branches,2,64
tive than TEOS, but the higher price and the associated health
which are weakly cross-linked, and it easily loses its shape and
hazards of TMOS turned TEOS the most common precursor
tends to crush, as the chains impinge on one another due to

among silanes.6,56,57 The detailed mechanisms of silica aerogel
internal movements. Hence, denser aerogels with small pores
synthesis are widely described in the available literature.58–62
are obtained aer acid catalysed synthesis.71 Under acidic
Table 1 summarises the typical properties of monolithic
conditions the hydrolytic reactions are favoured by proton
silica aerogels. However, each modied aerogel is unique,63 with
donors, which readily attack the oxygen atoms due to their
specic properties related to the synthesis conditions and used
partial negative charge, while in a basic medium the slow
precursors.
hydrolysis reaction is the rate-determining step.2,58 Under
alkaline conditions condensation is faster, due to the slightly
2.1 Hydrolysis and condensation/gelation positive charge of Si atoms in the presence of proton accep-
tors,58 and the hydrolysed species are readily consumed into
Sol–gel structures start from the hydrolysis of precursors and
larger and denser colloidal silica particles.2,58 Such structures
subsequent condensation into primary particles, evolving
are more prone to prevent network dragging and crushing
through the developing solution, and aggregating to form larger
caused by internal pressure, yielding lighter aerogels with
secondary particles, which link in a continuous network with
higher pore volume.71
liquid in the interstices.51
In summary, the porosity of silica aerogels can be tailored
The sol–gel chemical reactions can be summarised accord-
through the balance between the hydrolysis and condensation
ing to Scheme 1, where hydrolysis and condensation occur in
rates, by adjusting the initial pH according to a specic
a parallel way.
precursor.72 As an example, silica aerogel density can be so
The primary particles have diameters less than 2 nm and the
different as 150 kg m3 or 500 kg m3, depending on synthesis
secondary particles feature diameters around 10 nm or more.
conditions, respectively, in a basic or acidic medium.73
Gelation starts to occur when secondary particles link to each
The gelation or gel point is attained when a continuous
other, resulting in neck-regions between them, and a meso-
network is formed, and the solution no longer ows under the
porous network.44,51 These structures are shown in Fig. 1.
effect of gravity.
The pH value is a decisive parameter for the relative rates of
hydrolysis and condensation of alkoxysilanes, as outlined in
Fig. 2, for precursors of the type Si(OR)4. The condensation
reaches the minimum rate around pH 1–3, since the isoelectric 2.2 Ageing
point of silica is achieved at pH 2, and thus the electrical Chemical reactions of sol–gel chemistry still exist even aer the
mobility of silica particles is minimum.59,64 gel point has been reached. The liquid inside the pores contains
Under acidic conditions, the hydrolysis reaction occurs at small particles, which are able to condense, as well as
higher rate and the condensation/gelation is the rate- wandering monomers that will join the network.2,74 That
determining step, favouring the simultaneous formation of continuous process of cross-linking and coarsening due to the
small oligomers with reactive Si–OH groups. This leads to additional condensation is the so-called ageing.75,76
Table 1 Typical properties (range of values) of silica aerogels
Property Units Range values References
Bulk density (rb) kg m3 3–500 Hüsing and Schubert;2 Kocon et al.66
Skeletal density kg m3 1700–2100 Hüsing and Schubert2
Mean pore diameter nm 10–150 Hüsing and Schubert;2 Han63
Porosity % 80–99.8 Hüsing and Schubert;2 Anderson
and Carroll67
Specic surface area m2 g1 200–1600 Hüsing and Schubert;2 Boday et al.68
Thermal conductivity (at 25 C) mW m1 K1 12–30 Han;63 Lu et al.69
Refractive index — 1.01–1.24 Hüsing and Schubert;2 Pierre
and Rigacci4
Young's modulus MPa 0.01–100 Hüsing and Schubert;2 Han63
Poisson's ratio — 0.2 Han63
Sound velocity m s1 20–1300 Han;63 Groß et al.70
This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 22768–22802 | 22769
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Journal of Materials Chemistry A Review
During drying, there are two major factors affecting the shape
of the solid porous structure of the gel. The rst relates to the
almost inevitable partial collapse of the network, as even the
smallest shrinkage in the interior of the gel body causes a pressure
gradient that results in cracks; second, the pore dimensions are
different throughout the network, and hence neighbouring pores
with different radii show different receding rates of menisci (faster
on bigger pores). Thus, the walls between pores of different
dimensions endure uneven levels of stress and therefore tend to
crack due to the unbalanced forces.75,81

There are several drying techniques, namely, supercritical
drying (SCD), freeze-drying, and ambient pressure drying (APD).
Along with the gel's composition, the drying of the gels dictates
Fig. 1 SEM image of a native silica aerogel with the schematic
representation of primary and secondary particles (reprinted from ref.
pore dimensions and their overall textural properties, and thus
44, copyright 2014, with permission from Elsevier). the chosen method is of high relevance.80,82 While bre-
reinforced aerogels can be dried under ambient pressure with
good results, native silica aerogels are prone to collapse and lose
their monolithic shape.83 In fact, the embedded bres act as
a supporting skeleton, preventing the aerogels' shrinkage
caused by the drying capillary pressures.37,47
Table 2 highlights the inuence of drying conditions on the
characteristics of silica aerogels: for a similar fraction of
embedded bres, SCD favours lighter materials (3 to 11%).83,84
APD can be tuned to be a suitable cost-effective alternative:
for example, the volume shrinkage of silica aerogel composites
reinforced with a micro-glass bre mat was reduced from
z62% to z22%, following a gradient multi-segment drying
process aer a surface treatment,85 as described in Table 2.
All the composites listed in Table 2 exhibit characteristics of
super-insulating materials, designated as such when the
thermal conductivity is inferior to 20 mW m1 K1, measured at
standard pressure and temperature.86
Fig. 2 Rate of hydrolysis and condensation reactions of tetra alkox-
ysilanes with regard to pH dependency (adapted and reprinted with
2.3.1 Supercritical drying. SCD is the ideal method for
permission from Springer Nature: Springer-Verlag, Chemistry Spectros- drying the gels, in order to obtain aerogels with lower density.87
copy and Applications of Sol-Gel Glasses, from ref. 65, copyright 1992). The technique consists of removing the solvent inside the pores
under supercritical conditions in order to avoid capillary pres-
sures, since the liquid–gas interface is suppressed. Therefore,
Ostwald ripening refers to the phenomenon occurring at the the change in the dimensions of silica gels subjected to super-
micro level during ageing, in which the existing small particles critical drying is mainly due to the ageing stage.83 The main
with unreacted sites (OH moieties) tend to dissolve and repreci- disadvantages of SCD are the high complexity of the equipment
pitate into larger particles, or condense into more favourable required to operate at high pressure and the signicant cost of
regions of secondary particles, such as pores or crevices, particu- the process.9,39,41–43,46
larly in the necks between them.2,77 The micro-level condensation In supercritical approaches, the solvent can be removed by
leads to additional stiffness of the gels, which causes contraction two different procedures: (i) the high-temperature supercritical
of the network and withdrawal of some solvent from the pores; drying, in which the synthesis solvent is vented aer surpassing
this dimensional change is called syneresis.78 its critical point (rst introduced by Kistler in 1931 88); and (ii)
The ageing, occurring at pH between 8 and 12, will deter- the low-temperature supercritical drying, in which the synthesis
mine the extent of shrinkage at the drying stage.79 A silica matrix solvent is exchanged with a suitable and soluble solvent system,
strengthened by adequate ageing will better resist the drying generally supercritical CO2 (introduced by Tewari et al.89 in
capillary pressures,79 allowing an improvement of approxi- 1985). Since CO2 features a mild critical point (31.1 C and 73.9
mately 2-fold in the modulus of elasticity.44 bar 90), it is oen used for exchanging the synthesis solvent in
the pores or dissolving it, allowing SCD to be conducted at low
temperature. In this way, the main advantages of SCD in terms
2.3 Drying of lack of capillary pressures are maintained,80 also providing
The ultimate goal of the sol–gel drying process relies on the the possibility of drying organic–inorganic matrices without
solvent removal from the matrix by maintaining the gel network, degradation.91 Yet, solvent exchange can be a rather lengthy
yielding a porous solid with unchanged volume and shape.80 process, since it depends on the size of the gel.92 So, studies
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Table 2 The influence of drying techniques on the final characteristics of silica aerogel composites (obtained from TEOS85 and polyethoxydisiloxane (PEDS), a TEOS pre-polymerized were carried out on the development of methods to reduce the
Markevicius et al.83
Martinez et al.84
time for aerogel manufacturing, based on rapid supercritical
extraction. This process (which includes gelation, ageing and
Jiang et al.85
References
drying), carried out in moulds at high-temperature and pres-
sure, yielded aerogels within hours (<5 hours) rather than
days.93,94 Aerogels with superior mechanical properties were
produced, displaying a 3-fold higher elastic modulus compared
to the low-temperature SCD aerogels.93 However, this method
Thermal conductivity
has a signicant impact on the reaction kinetics, leading to the

(e) 13 (at 200 C) formation of bigger silica particles, with larger necks and, thus,
17.5 (at z20 C)

16.6 (at z20 C)
14.1 (at z20 C)

16.0 (at z22 C)
13.9 (at z22 C)
(mW m1 K1)
with low specic surface area.93,95

2.3.2 Freeze-drying. Under reduced pressure and tempera-
ture, a solvent can be evacuated by lyophilisation, avoiding the
(d) —
(b) —
(a) —
(c) —
liquid-phase meniscus stresses. By a fast freezing of the solvent,

—
using liquid nitrogen, followed by its sublimation under vacuum,
it is possible to avoid the skeleton's shrinkage and, consequently,
obtain highly porous aerogels.25,80 The process is commonly
rb (kg m3)
applied to drying hydrogels,96 since the solidication of water is

(d) 138
(b) 219
(a) 248
(e) 129
(c) 171
more readily accessible than for usual organic solvents.

125
121
101
114
100
The lyophilisation cycle encompasses three steps: (a)

—
lowering the temperature of the solvent (inside the pores) below

its triple point; (b) evacuation of the system until vacuum; and
(c) controlled sublimation under isobaric conditions.80 The
Volume shrinkage (%)
process is prone to the formation of microcrystalline salt-like

structures within the samples, since micro-regions with differ-
ences in freezing and sublimation rates can appear.80,95 As
Collapsed
a result, pore size tends to be augmented, compared to the case

(d) 26.3
(b) 55.3
(a) 62.2
(e) 22.4
(c) 38.3
of SCD.95
3.2
2.3
10
19
Clay based aerogels are generally dried by freeze-drying. It is

7
generally accepted that, during the drying process, a rearrange-

ment of clay layered sheets occurs which leads to lightweight
(c) 50 C, 5 h + 100 C, 24 h
aerogels.97,98 This kind of material fullls the needed features of

(d) 50 C, 5 h + 180 C, 8 h
(b) 50 C, 5 h + 80 C, 24 h
ame retardant materials.99–101

APD (ve alternatives)
(e) 50 C, 8 h + 80 C,
2.3.3 Ambient pressure drying. The simple evaporation at

24 h + 180 C, 8 h
Drying technique
ambient pressure seems to be the most obvious method to

(a) 100 C, 24 h
remove the solvent from a porous material, by raising the

8 h + 100 C,
temperature above the solvent’s boiling point and turning it

CO2 SCD
CO2 SCD
CO2 SCD
into a gas – this is the basic principle of APD.80

APD
APD
APD
The solvent within the system coexists in three states: the

liquid lling the pores, the liquid–gas transition phase, and the
gas phase. The receding menisci in the pores induce high
capillary pressures, reaching hundreds of bars within the
Surface treatment
HMDZ/n-hexane
nanopores, and cause cracks in the structure.80 Oen there is

a loss of the monolithic shape, when capillary pressures during
(at 50 C)
drying surpass the elastic limit of the solid structure, generating

HMDSO
HMDZ
HMDZ
granular aerogels.43,83 This is particularly signicant with pore

sizes smaller than 80 nm. The term “xerogel” denes
a shrunken gel. Indeed, APD usually generates xerogels, either
in the granular form or as impregnated composites (such as
Polyethylene terephthalate
bres of 2–4 mm diameter
mats or blankets).80 The volume of the xerogel is reduced by

Microglass matting, with
a factor of 5–10, compared to the dimensions of the gel.102

(unknown fraction)
Tencel® (25 wt%)
Reinforcement
(9.1 volume%)
(PET) blanket
2.4 Strategies to minimize APD shrinkage

solution83,84)
APD is an advantageous drying technique when taking into

None
account the involved costs, the low hazard levels and suitability
for large-scale commercial applications.46,103,104
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In order to prevent irreversible densication or partial Finally, the embedment of bres and nanobres is recog-
collapse due to stresses generated by capillary pressures, the nized as an effective method of strengthening silica aero-
preparation of aerogel-like APD materials requires specic gels,46,119–121 since the monolithic shape is preserved due to
adaptations, consisting of both chemical surface modication bres, in spite of the inevitable fractures (both at micro and
and skeleton strengthening.37,80 macro levels) occurring during evaporative drying.83
The condensation of reactive groups in the network surface, The shrinkage and strengthening of wet gels have been, for
mainly Si–OH, causes a gradual shrinkage that leads to the a long time, a widely researched topic.30,44,51,59,122,123 For more
ensuing densication. Those reactions can be prevented aer details, the pioneering investigation of Phalippou et al.,123 the
a surface treatment, carried out with reactive alkylsilane NASA Tech Brief of Paik and colleagues30 and the review work of
compounds, with non-hydrolysable Si–R alkyl groups,12,80,105,106 Maleki and co-workers44 are a convenient basis.
as is the case of HMDZ (hexamethyldisilazane) or HMDSO
(hexamethyldisiloxane) (vide Table 2). 2.5 Insulation properties of silica aerogels
An increased concentration of hydrophobic moieties directly The extremely low thermal conductivity and the inorganic
attached to the silicon atom, such as methyl groups, can lead to nature (non-combustible) of silica aerogels turned them into
reversible shrinkage, the so-called ‘spring back’ effect.107–109 It ideal substitutes for traditional insulating materials, such as
consists of a mechanical expansion of the gel network, which polystyrene or polyurethane foams.124–127 Currently, rock wool
recovers almost to its original volume, as can be seen in Fig. 3. and glass wool are commonly used, and despite their inorganic
The phenomenon occurs during the last stage of the drying, nature, higher insulation performances are only achieved aer
when the porous structure is able to endure the drying loads, increased thickness.127,128 Fig. 4 depicts the typical values of
and the spring-back effect is driven by the repelling of hydro- thermal conductivity of some insulating materials, along with
phobic functional groups.43,109 those for the free air and an aerogel. Additionally, other
The use of precursors with hydrophobic character, such as important aspects have to be considered: while aerogel based
methyltrimethoxysilane (MTMS), with a non-hydrolysable thermal insulation materials require less than half of the
methyl group, also prevents the collapse of gels during drying thickness, when compared to other inorganic-based materials
and imparts higher exibility to the matrices.35,107 or polymeric foams, aerogels are much more expensive, around
Hybridization, through the incorporation of polymers in 8–9 times more expensive than conventional materials.115
the silica backbone, is another technique of aerogel rein-
forcement that prevents shrinkage. It consists in the cross-
linking of the network by adding monomers (e.g., acrylates
and cyanates), leading to increased exibility and/or
mechanical strength of the hybrid material.44,110–115 These
aerogels are oen termed X-aerogels.116,117 However, as
a consequence of the effective mass addition, the cross-linked
gels tend to feature lower porosity, a detrimental outcome that
leads to higher density materials, and a decrease of surface
area,118 along with the inevitable penalization of the thermal
conductivity.115
Another strategy consists in operating with drying control
chemical additives, such as glycerol, formamide, dimethyl
formamide, or tetramethyl ammonium hydroxide, added
during the initial phase of silica gel synthesis. Their function is
to promote the uniformity of pore size dimensions, thus mini- Fig. 4 Average and limit values of thermal conductivity for conven-
mizing stress asymmetries.80 tional insulating materials, free air and a silica aerogel (data summar-
ised from ref. 139–141).
Fig. 3 Silica aerogel composites synthesised with polymethylsilsesquioxane precursors and dispersed boehmite nanofibres, under ambient
pressure drying conditions: a temporal shrinkage followed by re-expansion can be observed, due to the spring-back effect (reprinted with
permission from ref. 138. Copyright 2016, American Chemical Society).
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According to a study sponsored by the European Commis- of vibrational energy levels of interatomic bonds or even by free
sion, the use of aerogels as building insulation materials was electron transport under thermal gradient.143,144
estimated to reduce 30% of overall energy consumption and Heat conduction in the gaseous state exists due to the colli-
25% of CO2 emissions, yet providing the same comfort level.129 sions between molecules, since the faster ones transfer part of
Moreover, silica is the most abundant compound on the their kinetic energy to the slower molecules.144 However, those
Earth130 and the current environmental issues, such as limited movements are of minor relevance in the monolithic native silica
energy resources,131 emphasize the aerogel application. These aerogels, since the average pore dimensions are typically below
materials, being amorphous, have no hazardous effect either for 70 nm,133 and the mean free path of air molecules at 1 atm and
human health or to the ecosystems.124,132 23 C is around 66 nm.145 The Knudsen effect describes the
Heat transfer in monolithic non-evacuated aerogels involves reduced diffusivity directly linked to the pore dimensions, when
three components,131,133,134 since the convection heat transfer each gas molecule collides more frequently with the pore walls
can be neglected in porous materials where void spaces are than with neighbouring molecules,146,147 leading to a reduced
smaller than 4 mm.135,136 Thus, the total thermal conductivity energy transfer through the gas molecules.147
can be described using eqn (1). The radiative thermal conductivity relates mainly to the
spectral mass attenuation coefficient, e. While the solid and
kT ¼ ks + k g + kr (1) gaseous thermal conduction requires a medium, the radiative
thermal conductivity is based on electromagnetic waves,
where kT is the total thermal conductivity and ks, kg, and kr refer, correlated to the photon's mean free path.148 Therefore, this
respectively, to the solid, gaseous and radiative transfer component is highly temperature-dependent, with a high
components of the rst. factor-scaling exponent.144 According to Fomitchev et al.,3 the
Aerogels, with a signicant fraction of small pores, have also radiative thermal conductivity of silica aerogels can be
a tortuous silica structure, which minimises both the gaseous computed according to eqn (5):
and solid conductivities. As an example, an aerogel with
a density of 40 kg m3, with circa 50% pores over 20 nm in kr ¼ 16n2sT331 (5)
diameter, typically exhibits a thermal conductivity of 18 mW
m1 K1 at ambient pressure; a denser silica aerogel (circa 100 where n is the index of refraction, s is the Stefan–Boltzmann
kg m3), with 80% pores with a diameter below 20 nm, displays constant, T is the temperature (K) and 3 ¼ rbe, the spectral
superior thermal insulation performance, namely 12 mW m1 attenuation coefficient.
K1 at ambient pressure.79 Fricke and colleagues137 rst estab- Silica aerogels display poor absorptive properties in the near-
lished relationships between silica aerogels' bulk density, rb, infrared region, particularly below the wavelength 5–8 mm.124,149
and the three components of thermal conductivity (eqn (2)–(4)), With a rise in temperature from 300 to 1000 K, the radiative
by varying aerogel density between 70 and 230 kg m3, as thermal conductivity can lead to an increase from 8 to 92% of
follows: the total conductivity of native silica aerogels.150
All the heat conductivity mechanisms within aerogels are
ks f rb1.5 (2) sketched out in Fig. 5.
kg f rb0.6 (3)
2.6 Mechanical properties of silica aerogels
kr f (rbe)1 (4)
The mechanical behaviour of native silica aerogels can be
where e is the spectral mass attenuation coefficient, an optical understood according to a proportionality that relates the
property related to the efficiency of a material to attenuate Young's modulus, E, with material's bulk density, rb,65
infrared radiation (IR).142 described using eqn (6).
The specic surface area (SSA) of silica aerogels is also useful
as an indicator of the thermal insulation performance of aero-
gels. For a given density, the smaller the size of the pores, the
higher the SSA, and the better will be the insulation perfor-
mance. This evidence was described by Wei et al.:136 a silica
aerogel with a density of 120 kg m3 and a surface area of 400
m2 g1 displayed a thermal conductivity of 20.1 mW m1 K1;
by increasing the SSA to 1000 m2 g1, the thermal conductivity
was reduced to 13.7 mW m1 K1. Since the SSA is more easily
assessed than the pore size distribution of the aerogels, SSA may
be a valuable parameter in this context.
The solid thermal conductivity relates to the solid fraction of
Fig. 5 Different mechanisms of heat transfer in aerogels: solid
aerogels, i.e., it is inuenced by the extent of crosslinking and conduction through the particle's chain (red arrows); radiative
network connectivity.133,134 Heat conduction in the solid conduction (wavy yellow arrows); and gaseous thermal conduction
network occurs through the atomic lattice, due to the excitation (blue arrows) (colours online).
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E f rbb, b z 3.2.3.8 (6) estimated from thermal diffusivity data as being 41 mW m1
K1,156 which can yet be considered a good result taking into
The manufacture technique is somehow relevant, since account the high density of isocyanate cross-linked composites.
aerogels synthesised under neutral or mild acidic conditions However, as detailed by Huang and colleagues,157 when
can be twice stiffer compared to similar density aerogels increasing the covalent bonds within a system, its thermal
developed under basic conditions. Suitable ageing and heat conductivity gets increased as well, since the direct contact
treatments can also improve aerogel strength.65 Nevertheless, between neighbouring particles is augmented.
even aer optimizing synthesis conditions, silica aerogels are When lighter materials are sought, by encompassing
brittle materials, with a friable nature derived from their ionic- a balance between moderate mechanical properties and supe-
covalent bonds and high porosity.80,151 rior insulation performance, this can be better accomplished
Mechanical characterization of native aerogels is oen through silica aerogel reinforcement with bres, as disclosed in
a difficult task, either in terms of the specimen preparation or this literature review. Aerogel companies like Aspen Inc., Cabot
precisely measuring the small load forces applied.63,117 There- Corporation, and Nano High-Tech Co., Ltd. grant further proof by
fore, the evaluation is typically performed in compression and producing aerogel blankets.158
exural modes.80,117 Moreover, the tensile strength of aerogels The appropriate bre fraction along with their homogeneous
can be deduced from the three-point bending exural test.117 dispersion will potentiate improved mechanical and/or insu-
The compressive response behaviour of aerogels can be quite lation properties,57 turning this into a versatile route to facilitate
diverse: at higher densities, they tend to shatter aer very little aerogel manufacture.46,159–161 Additionally, the use of recycled or
strain, exhibiting glass-like behaviour; at smaller densities, in the waste bres23,83 to strengthen silica aerogel composites is being
range of 80 to 150 kg m3, silica aerogels can withstand studied at the laboratory scale, paving the way towards
compression up to 70% strain and recede back to the original sustainable and lower cost materials,40 with almost unlimited
volume.80 A silica aerogel of 100 kg m3 subjected to the three-point potential for further development.162
bending exural test can sustain a maximum load of 0.02 MPa.117 There is a broad consensus (either among the scientic
The integration of bres has been evidenced as an effective community or aerogel industry enterprises) about bre
way to improve aerogels' mechanical performance, either embedment as being the most versatile and effective method of
during drying or in response to stress loads. As reported by silica aerogel strengthening.30,46,119–121,155,158
Zhihua and co-workers,152 aer the incorporation of 10 wt%
ceramic bres (Al2O3: z43–45%; SiO2: z49–52%; zFe2O3: 0.5–
0.8%), the compressive strength of the reinforced aerogel 3.2 Techniques for preparation of silica aerogels with bres
increased six-fold in comparison with the pure silica aerogel, There are several techniques reported in the literature to rein-
while the thermal conductivity (measured in air at room force silica aerogels with bres. The pioneering investigation of
temperature) just increased from 23 to 29 mW m1 K1. Wang et al.133 consisted of the incorporation of ceramic bres,
Regarding the effect of bres on aerogel's properties, to further improve the radiative properties of doped aerogels
a detailed discussion is presented in the next section. due to their opacifying effect (mainly for high temperature
applications), also providing extra strength to reduce their
inherent fragility.133 Such composites were (and still are)
3 Silica-aerogels with embedded
accomplished with dispersion of the bres in the sol prior to the
fibres onset of gelation.47,163,164 The mixture is then poured into
a mould for gelation, and this procedure is typically used to
The embedment of bres in silica aerogels can, to a large extent,
manufacture strengthened and denser materials.51,163
prevent the shrinkage during their drying,30,47,83 being as well an
This procedure is briey sketched out in Fig. 6a. The loading
effective way to improve their mechanical properties.30,51,153,154
reinforcement limit is imposed by the uniformity of dispersion,
The challenge is, in spite of the reinforcement, to preserve their
since aggregates or bundles due to an excess of bres might
inherent insulation properties and high specic surface area.
create weakened sites and decrease insulation performance of
composites. This is more critical when using inorganic bres.
3.1 Silica aerogel reinforcement strategies: a comparison Some contextual examples are presented in Sections 3.5 and 3.6.
Among the current known techniques of silica aerogel rein- Flexible aerogel composites are generally obtained by pour-
forcement (previously summarised in Section 2.4), chemical ing the sol over a bre batting previously placed within
cross-linking with reactive molecules or polymers leads to a container, as illustrated in the scheme of Fig. 6b. A basic
superior improvement in their mechanical performance.155 For catalyst is added, just immediately before or aer pouring the
example, the compressive strength of amine-modied silica sol, to induce the gelation within a few minutes.22,33,165,166 The
aerogels at the breaking point was 4.1 MPa, with a maximum protocol in which the basic catalyst is added before pouring the
strain of 5.7%; aer being cross-linked with isocyanate, the sol is preferential, because the bres may compromise the
mechanical strength at failure became improved by a factor of homogenization of the solution.
45 (186 MPa, 77% strain). However, such an extraordinary There are other versions for this route of composite prepa-
improvement came at the cost of increased density (190 vs. 478 ration: (i) alternating the pouring of the sol with deposition of
kg m3).156 The thermal conductivity of those composites was bres, several times, according to the number of planned
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are responsible for the interaction with silica.175 In addition, Li

et al.164 described the modication of the surface of sepiolite
bres, aer immersion in nitric acid aqueous solution, before
their dispersion in the sol. Strong composites were produced
due to the Si–O–Si chemical bonds between the bres and silica
matrix.
Apart from chemical bonds, other interfacial interactions
can also contribute to improving a system's inner adhesion.
Fig. 7 shows how, at a fracture (Fig. 7a), protruding aramid
bres were encircled by aerogel fragments (Fig. 7b), revealing

the electrostatic attraction between the aerogel matrix and
aramid bres.167 In another study of the same authors it was
better understood how, during gelation, aramid bre walls
acted as nucleation spots of the growing silica network matrix,
although FT-IR spectra of the composite revealed no additional
chemical bonds.121
Markevicius et al.83 also showed, with a clear SEM image of
cellulose–silica aerogel composites, a full detachment between
the intact bre and the fractured aerogel; the cellulosic bres
entrenched within the aerogel matrix sustained the structure
Fig. 6 Schematic procedures of silica aerogel composite syntheses:
and the monolithic shape of composites, and a low thermal
part (a) shows the addition of dispersed fibres to the silica sol; part (b) conductivity (less than 20 mW m1 K1) was preserved.83
refers to the approach where a web or mat of fibres previously fill the
mould, over which the sol is poured at the onset of gelation.
3.3 Inorganic and organic bres as reinforcement materials
of silica aerogels
layers;120 (ii) pouring all the alcosol into the mould and then The type of bre, its intrinsic features, such as strength, density,
immersing the bres layer by layer167,168 or (iii) pouring the sol length, diameter, length-to-diameter ratio, optical properties,
into a container and soaking a bre matting or entangled bres curvature, and orientation angle, as well as the fraction of bre
at the onset of gelation.169,170 content contribute to the ultimate features of silica aerogel
To obtain silica aerogel composites in the form of thin lms composites, impacting their mechanical performance and
with extreme exibility, an ideal technique of reinforcement insulation properties.176–179 Hence, the accurate selection of the
involves the addition of electrospun nanobres,166,171 since bre type is essential, in order to create synergies in the
there is an improved integration between the two phases.166 The conception of composites. For example, a thermal barrier for
embedment procedures can be accomplished by impregnating a high temperature environment must be manufactured with
a web previously formed172 or electrospinning the bres in thermally resistant bres that also have a large spectral complex
situ,166 fully integrating the sol through precise control of gela- refractive index throughout the infrared region;150 if some
tion time.166,173 A different procedure was described by degree of exibility would be needed, a exible bre should be
Mazrouei-Sebdani and colleagues:174 silica aerogel micro- used in the appropriate fraction.127
granules were added to an electro-spinning polyethylene tere- 3.3.1 Inorganic bres. The thermal stability inherent to
phthalate (PET) solution, yielding a silica aerogel–PET nano- inorganic bres, along with a low thermal expansion coefficient,
bre composite. propels their use as a structural reinforcement material of silica
3.2.1 Enhancement of bre–aerogel interfacial binding.
Chemical interactions between silica sol and the reinforcement
materials may occur, depending on their chemical composition,
leading to improved mechanical properties of composites. The
incorporation of bres or nanobres with the ability to react/
interact with silanol groups during gelation and ageing steps
can prevent the aerogel structure from collapsing during
drying.138 As reported by Hayase and co-workers,138 the hydro-
lysed MTMS preferentially adsorbs on and reacts with dispersed
boehmite nanobres at an early stage, favouring homo-
polycondensation on the bre surface. Chemical interactions Fig. 7 Interfacial bonding between aramid fibres and a silica aerogel:
were also reported by Bangi and colleagues.175 They observed (a) protruding aramid fibres at the silica aerogel composite's fracture,
suggesting the absence of chemical bonds; (b) aramid fibres sur-
silica particles tightly attached to the sidewalls of previously
rounded by silica fragments, evincing strong attraction between both
modied carbon nanotubes (CNTs). The modication of CNTs phases (adapted and reprinted from ref. 167, copyright 2016, with
with a surfactant provided OH groups on their surface, which permission from Elsevier).
Table 3 Silica aerogel composites reinforced with inorganic fibres: synthesis, and mechanical and thermal characterization
Journal of Materials Chemistry A
Thermal conductivity
rb (kg m3) Compressive strength (MPa) (mW m1 K1)
Synthesis precursor; catalyst; mode of
Reinforcement with inorganic bres bre addition; drying Neat Reinf. Neat Reinf. Neat Reinf. References
22776 | J. Mater. Chem. A, 2019, 7, 22768–22802

30 wt% TiO2 + 20 wt% kaolinite + 10 wt% TEOS; acid catalysed by HF; bres added 112 185 0.018 0.128 14 (100 C) 22 (100 C) Deng et al.163
attapulgite + 10 wt% ceramic bresa to the sol; ethanol SCD
Individually aligned glass bres, 5–20 mm TEOS; 1st: HCl, 2nd: NH4OH; bres 115 163 0.72 (50% strain) 3.70 (50% strain) 22 (25 C) 24 (25 C) Liao et al.119
diameter, 3 volume% added layer by layer permeated with sol;
APD, 70 C (12 h) + 100 C (8 h)
Sepiolite bres, 1.5 volume% TEOS; 1st: HNO3, 2nd: NH4OH; bres 200 210 0.1 1.1 21 (50 C) 25 (50 C) Li et al.164
dispersed in the sol; ethanol SCD
Silica bres, 10.5 wt% Sodium silicateb/MTESc (1/0.3) 1st: cation 125 104 —d 0.1 36e 22 (RT)f Shao et al.57
exchange, 2nd: NH4OH; bres added
to the sol; APD, 50 C (2 h) + 80 C (3 h)
+ 130 C (4 h)
Attapulgite bres, 2 wt% TEOS; 1st: HCl, 2nd: NH4OH; bres 188 173 —d 1.2 21.8 (RT)f 19.8 (RT)f Li et al.37
added to the sol; APD, 50 C (24 h) + 85 C
(2 h) + 125 C (1 h)
ZrO2 bers, 4–7 mm diameter, 300–500 TEOS; acid catalysed by CH3COOH; bres 160 290 0.36 0.82 23.5 (25 C) 26.2 (25 C) Hou et al.186
mm length, 10 wt% added to the sol; CO2 SCD
Aluminium borate whiskers, 0.5–1 mm AlCl3$6H2O/TEOS (1/0.33) catalysed at 150 350 0.26 1.40 27 (RT)f 40 (RT)f Hou et al.187
diameter, 15–60 mm length, 20 wt% 60 C; whiskers added to the sol; ethanol
SCD
a
Mixture of bres: Al2O3, 43–45%/SiO2, 49–52%/Fe2O2, 0.5–0.8%. b 6.2 wt% Na2O, molar ratio of SiO2 to Na2O ¼ 3.13. c Methyltriethoxysilane. d Compressive strength of unmodied silica aerogels
with SCD (rb ¼ 96 kg m3) is z0.04 MPa.188 e Thermal conductivity of a TEOS derived aerogel, aer multiple surface modications, dried under ambient conditions (pressure and temperature),
with an apparent density of 69 kg m3.189 f Room temperature.
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This journal is © The Royal Society of Chemistry 2019

Review
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aerogel composites, particularly in thermal barrier SCD.188 Nevertheless, lightweight and mechanically robust
systems.160,164,180,181 For very high temperature insulation, materials can be developed: reinforced silica aerogels with
ceramic bres are the most suitable to embed in aerogel 2 wt% attapulgite bres endured a compressive strength of
composites, while organic bres must be excluded; also, 1.2 MPa 37 (an increment by a factor of 12 in comparison to
carbon-based bres can't be an option, as they degrade above aerogel composites reinforced with 10.5 wt% silica bres).
300 C.182 According to the work of Li et al.,37 appropriate inorganic
Silica bres are a typical example for demanding environ- bres, even in a small amount, can be able to prevent aerogel
ments,79 remaining stable under extreme conditions:160,180 they densication during ageing and drying, while better insulation
exhibit a limit of temperature stability around 1100 C, being and/or mechanical performance can also be achieved.
able to surpass that limit for small periods of time.180 By means Recently, Wang and colleagues190 developed a new technique
of suitable manufacturing conditions, microporous bres with of manufacturing ceramic nanobres with controllable diame-
skeletal densities as low as 1.5 g cm3 can be achieved, allowing ters, from 47 to 815 nm. In general, the methodology consisted
a diminished weight of the nal composites, a determinant pre- of a solution of solvent/precursor that is pumped and forced out
requisite in the aeronautics and space engineering elds.180,183 by airow, through a small aperture, collected in the form of
An additional and important feature of porous silica bres is entangled nanobres. Quite promising results were reported in
their effective electrical insulation.180 the synthesis of large-scale 3D sponges composed of titania
If silica aerogel composites are envisioned to perform in (TiO2), zirconia (ZrO2), or yttria-stabilized ZrO2 (YSZ), with
oxidising atmospheres at temperatures above 1400 C, the bre densities ranging from 8 to 40 kg m3. Moreover, due to the
reinforcement material has to be made from oxides with very inorganic nature of the blow-spun nanobres, this web can be
high melting point, among which a-alumina encompasses all used at extremely high operating temperature (the mechanical
the features, including the advantageous refractory property.182 resilience of the YSZ nanobre sponge was observed even at
Other ceramic bres, such as Al2O3, Fe2O3 based, or of alumina– 1300 C).190
silica type, also incorporate the needed features to integrate 3.3.2 Organic bres. This type of bres is mainly used to
high performance thermal barriers, and generally are not impart higher exibility to aerogels160,167,172,191 (Fig. 8), yet
sensitive to environmental attack.181 As inorganic bres are providing reinforcement/reduced shrinkage during drying.42,83
thermally resistant,184 they are less prone to deteriorate in high The high length-to-diameter ratio imparts better exibility to
temperature environments compared to organic high- the organic bres, compared to the inorganic natural bres,
performance synthetic bres.185 Therefore, a broader oper- which is an advantageous feature for the manufacture of exible
ating temperature is allowed when aerogels are reinforced with aerogel composites.172
inorganic bres.117 When robustness must coexist in tandem Natural bres are viewed as environmentally favourable
with insulation performance, there is an upper limit of inor- substitutes of synthetic polymers for reducing the carbon foot-
ganic bre loading in order to attain optimal properties of silica print of industrial products.83,84,155 Notwithstanding, organic
aerogel composites. This issue is better explored in Sections 3.5 natural bres are not frequently used as silica aerogel rein-
and 3.6. forcement materials. Cotton is the most reported one, either
A brief compilation regarding studies of silica aerogel used as textile structures33,169,192 or as raw cotton.44,193,194 Flax and
composites reinforced with inorganic bres, by selecting those kenaf organic natural bres are also mentioned in the devel-
in which the differences between them and the native aerogel opment of silica aerogel composites.195,196
are disclosed, is presented in Table 3. How the bres addition Several studies demonstrated the versatility of cellulosic
affects the mechanical and thermal behaviour can be seen by bres (both on the nano- and micro-scale), providing rein-
the comparison of results between “Neat” (refers to a pure silica forcement of silica–cellulose aerogels for SCD, APD or freeze
aerogel) and “Reinf.” (refers to a silica aerogel composite rein- drying routes.38,42,83,169,191,197 The broad availability and low cost
forced with the indicated bres).
As a general trend, an increase in the bulk density due to the
bre addition is observed, along with a signicant improvement
of the composites' mechanical properties compared to the
native silica aerogels. On the other hand, the insulation prop-
erties tend to become slightly damaged.
However, this is not always the case. According to the results
of Shao et al.57 and Li et al.,37 exceptional insulation properties
can be achieved in aerogel conception through the composite
approach, with thermal conductivity values in the range, or even
below those of air. Moreover, lighter materials can be manu-
factured by ne-tuning of bres addition. Fig. 8 Examples of flexible silica aerogel composites reinforced with
organic fibres. (a) Cellulose–silica nanocomposite aerogel reinforced
But, if the reinforcement material is still silica, mechanical
with regenerated cellulose fibrils (SCD) (reproduced with permission
performance can only be moderately increased. Shao et al.57 from ref. 191, copyright 2012, John Wiley and Sons); (b) silica aerogel
reported an improvement of compressive strength by a factor of composite reinforced with electrospun polyvinylidene fluoride fibres
2, compared to the native and unmodied silica aerogels with (APD) (reproduced from ref. 172, copyright 2013).
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of cellulose bres, combined with APD drying, enable a facile

way to develop highly efficient composites.
According to the available literature, the rst organic bre
embedded in silica aerogels was synthetic polypropylene, in
a nonwoven structure reinforcing an adsorbent material.154 The
composite was developed to remove hazardous chemicals from
air and sewage disposal, or even for medicine ltering. A surface
treatment with trimethylchlorosilane turned the aerogel
composite hydrophobic, with a contact angle of 135 . The
Examples of fibre-reinforced silica aerogel composite micro-
Fig. 9
addition of bres decreased the aerogel's adsorptive perfor- structures: (a) with electrospun fibres from PDMS-based polyurethane
mance but improved the mechanical behaviour of the (reprinted with permission from ref. 166. Copyright 2009, American
composite, allowing its use in practical applications. However, Chemical Society); (b) appearance after fracture of silica aerogel
according to the authors, these silica–polypropylene aerogel composites reinforced with PDMS-based polyurethane electrospun
fibres (reprinted with permission from ref. 166. Copyright 2009,
composites performed better than conventional adsorbing
American Chemical Society).
materials in the adsorption of benzene, methylbenzene or
carbon tetrachloride.154,198
Electrospinning is one of the last developed techniques for
oligomers, with molecular weights of 538, 1350 and 2973 Da. A
aerogel reinforcement by means of organic engineered micro or
lm with a thickness of 0.86 mm and a density of 172 kg m3
nanobres.160 It is an accessible technique172,199 to produce
(50 wt% nanobres and PDMS Mw of 538 Da) exhibited a very
bres with diameters as thin as 150 nm,200 much smaller than
low thermal conductivity of 13 mW m1 K1, a typical value of
cotton diameter, the most consumed natural bre,201 with an
pristine silica aerogels. Another lm with a thickness of
average value of 10 mm.201 The technique can be applied to
0.46 mm and a density of 79 kg m3 (40 wt% nanobres and
almost any soluble polymer with a molecular weight large
PDMS Mw of 1350 Da) featured the worst performance in
enough to form long chains.202
thermal conductivity, with 51 mW m1 K1, around twice the
Briey, in the conventional nanobre procedure, the poly-
thermal conductivity of air. The difference in thermal conduc-
mer is dissolved in a solvent in order to achieve precise viscosity
tivity between both materials was attributed to the molecular
to yield continuous nanobres (low viscosity results in droplets
weight of PDMS, as a higher fraction of PDMS but with lower
that solidify as nanoparticles), then it is jetted through a capil-
molecular weight leads to homogeneous mesoporosity, a bene-
lary spinneret under the inuence of an electrostatic eld, and
cial feature for insulation performance.166
nally deposited in the form of a web in a collector support or
The major breakthrough of silica aerogel composites with
directly into the sol cast.166,172
electrospun bres is the possibility of producing aerogel
The diameter of conventional bres embedded in silica
composites as thin lms with astonishing exibility and improved
aerogels is signicantly higher than the typical dimensions of
response to fracture, as depicted in Fig. 9b. Even when subjected
pores or silica secondary particles, and despite the effectiveness
to a stress load that leads to fracture, the morphology of the tiny
of the reinforcement material, such a difference can lead to
nanobre network can to some extent sustain the composites. The
unbalanced responses to received stress loads. The smaller
cracked aerogel remained bridged by the nanobres, thus pre-
diameter of electrospun bres increases the adhesion between
venting the composite disintegration.166
phases, with smooth joints between the aerogel and the bres,
Although the pioneering studies on electrospun bres
as can be seen in Fig. 9a. The tight adhesion can then potentiate
embedded in silica aerogels need further development to
the stability and strength of monolithic aerogels, while
improve insulation efficacy and to scale-up manufacturing
enhancing their exibility.172 On the other hand, a higher
processes,172,203–205 technical applications such as protective
degree of contact can have a detrimental effect in terms of solid
clothing203 or super-capacitors205 are foreseen and being studied
thermal conductivity, but the smaller diameter of the nano-
by the scientic community.
bres extends the corresponding specic surface area, which is
Organic man-made and natural bres are preferentially used
advantageous to shield heat radiation.172
in aerogel composites conceived for operating at room
Wu and colleagues172 developed a exible silica aerogel
temperature, or in moderately high temperature environments,
composite, with a density of 202 kg m3, reinforced with elec-
since the low temperature degradation of the embedded bres
trospun polyvinylidene uoride nanobres (PVDF) (see Fig. 8b),
imposes such a restriction. For example, unmodied poly-
still maintaining good insulation features (see Table 4). The
propylene bres’ melting point starts at z150 C,206,207 and
authors attributed the relatively low conductivity of the material
these bres are oen used as aerogel reinforcement materials
to the diameter of nanobres, which is between 20 and
because of their high abrasion resistance207 and hydrophobic
200 nm.
properties (surprisingly, a polypropylene–silica aerogel
The work authored by Li et al.166 focused on the development
composite dried at 200 C is reported in the literature 154).
of TEOS based aerogel composite lms reinforced with poly-
High performance organic bres can extend the operating
urethane (PU) electrospun nanobres (500 nm diameter), in
temperature of silica aerogel composites. As an example, poly-
which polydimethylsiloxane (PDMS) was added to the sol prior
benzimidazole (PBI) is known for its extreme thermal
to the gelation event. The study covered different PDMS
Review
Table 4 Silica aerogel composites reinforced with organic fibres: synthesis, and mechanical and thermal characterization
Thermal conductivity (mW

rb (kg m3) Compressive strength (MPa) Bending strength (MPa) m1 K1)
Reinforcement with Synthesis precursor; catalyst;
organic bres mode of bres addition; drying Neat Reinf. Neat Reinf. Neat Reinf. Neat Reinf. References
This journal is © The Royal Society of Chemistry 2019

Polyvinylidene uoride TEOS; 1st: HCl, 2nd: NH4OH; 100a 202 0.75 5.23 0.02b 1.1 24 (RT)c 27 (RT)c Wu et al.172
(PVDF) electrospun PVDF web added to the silica
nanobres, 28 wt% PVDF sol; APD, 70 C (12 h) + 100 C
(12 h)
Nanobrillated cellulose PEDSd NH4OH; nanobres 75 131 z1 z2 — — 13.8 (RT)c 14.2 (RT)c Wong
water suspension, 2.28 g added to the sol; CO2 SCD et al.125
L1
Pectin nanobres, z6.7% Sodium silicate solution 110 (at pH 190 (at pH z1.4, 80% z34, 80% — — 17.4 (25 C; 16.2 (25 C; Zhao et al.155
methoxy groups and (26.5% w/w SiO2); NH4OH; 2.5, broke at 1.5) strain (at pH strain (at pH RHe 50%) RHe 50%)
20 wt% pectin content bres added to sol (pH 1.5); pH 1.5) 2.5) 1.5)
CO2 SCD
Aramid bres, KEVLAR®- TEOS 1st: HCl, 2nd: NH4OH; 100a 142 1f(E) z0.14(E) 0.02b z0.20 17–21 (25 C) 23.6 (25 C) Li et al.121
49, length > 10 cm, bres added layer by layer,
z6.5 wt% aer the sol; APD, 80 C (8 h) +
100 C (8 h)
Lyocell bres (Tencel®), PEDSd NH4OH; sol poured over —g (APD), 123 (APD), — — —g (APD), 0.106 (APD), —g (APD), 16.6c (APD), Jaxel et al.42
z8 mm length, z26 wt% loosened bres; APD 140 C (2 103 (SCD) 125 (SCD) 0.046 (SCD) 0.184 (SCD) 14.2c (SCD 17.5c (SCD)
h) & CO2 SCD
a
Typical value for bulk density of native silica aerogels.2 b Typical value for bending strength of native silica aerogels with density z100 kg m3.211 c Room temperature. d A solution of pre-
polymerized oligomers of TEOS, a SiO2 content of 20 wt%, in ethanol. e Relative humidity. f Typical value for elastic modulus (E) of native silica aerogels with a density of 100 kg m3.2 g Pure
silica aerogel collapsed during APD drying.
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Journal of Materials Chemistry A
J. Mater. Chem. A, 2019, 7, 22768–22802 | 22779

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resistance: it does not exhibit melting temperature, and the ageing and drying processes) was around 20%, whereas with the
onset decomposition temperature is 450 C in air (1000 C in an addition of 25 wt% cellulosic bres, a reduced shrinkage of
inert atmosphere).184 Remarkably (according to our literature z7% was achieved.
search), PBI hasn't yet been used as an aerogel reinforcement During drying, the embedded bres also act as an effective
material. On the other hand, m-aramid33 or p-aramid121 bres, skeleton frame that hinders shrinkage, since the casting volume
whose melting/decomposition temperature varies from 375 to is split into sub-volumes dened between two adjacent bres.
560 C,184 are already used as silica aerogel reinforcement The internal movements of silica chains are inhibited, while the
materials.33,121 drying stresses are limited to small units, instead of one unit
A selection of studies on aerogel composites reinforced with comprising the full body of the aerogel. Pure silica aerogels
organic bres is summarised in Table 4. Again, it was intended supercritically dried may undergo a linear shrinkage of around
to address a broader perspective of how the bre addition 5–10%, while the integration of bres can reduce the shrinkage
affects mechanical and thermal behaviour of silica aerogels, to neglectable levels.30,83 As an example, the difference in the
observed by comparison of results between “Neat” (refers to drying linear shrinkage (gel diameter) between a silica aerogel
a pure silica aerogel) and “Reinf.” (refers to a silica aerogel composite reinforced with silica bre felt and the pristine
composite reinforced with the indicated bres). counterpart (both supercritically dried in acetonitrile, at 295 C
Regarding the results of those selected studies, the addition and 5.5 MPa) was around 13%, and the reinforced aerogel had
of structural reinforcement materials in silica aerogels leads to no apparent shrinkage.30 Shrinkage in silica aerogel composites
an increased density. As a consequence, the ability to sustain mainly occurs through thickness (z axis),79,212 while monolithic
load is signicantly increased aer organic bre addition. non-reinforced aerogels shrink isotropically.79
The decreased value of elastic modulus compared to that of Paik and colleagues30 refer to the composite density as being
native silica aerogels (see the work of Li et al.121) denotes the typically about 10% higher than the density of the corre-
increased exibility of reinforced composites. More impor- sponding neat aerogel. In general, the mere addition of bres
tantly, silica aerogels can be substantially reinforced without will lead to increased density, as listed in Tables 3 and 4. Several
compromising their inherent insulation properties, in light of authors thoroughly addressed this issue, by studying the effect
the presented results of thermal conductivity, before and aer of different fractions of bres embedded in silica aerogels, and
the reinforcement. As expected, the best results were achieved dissimilar outcomes are described below.
aer the SCD route (see the work from Wong et al.125 and Zhao Markevicius and co-workers83 developed silica aerogel
et al.155); the challenge consists of further improvement of silica composites reinforced with Tencel® bres (diameter of ca. 10
aerogel composites via the APD route, towards cost-effective and mm and length z 2 mm). Tencel® is a commercial designation
efficient materials. of a man-made cellulosic bre, produced through the Lyocell
process. The precursor was PEDS (pre-polymerized TEOS), and
the gels were subjected to silylation in an HMDZ solution, for
3.4 Inuence of bres on shrinkage and density of silica 72 h. According to their results, the higher the bre content, the
aerogel composites smaller the shrinkage (Fig. 10a), in contrast to density, which
Gel shrinkage is a key factor concerning the bulk density of increased with increasing the bre fraction (Fig. 10b). A similar
aerogels. In fact, shrinkage or densication starts during trend was observed for aerogels obtained both by SCD and APD,
crosslinking reactions when silica particles coalesce to form but shrinkage also depends on the drying technique. The re-
larger necks.79 Shrinkage continues during ageing, when the ported values are the cumulative shrinkage of the ageing and
silica matrix develops mechanical rigidity, with clusters drying steps; while aerogels supercritically dried mostly shrunk
restructuring due to the silica dissolution and re-deposition during gel ageing, the evaporatively dried gels suffer additional
phenomena, which provides better resistance to the drying densication due to the capillary pressures during drying
process,79,83 as previously described. (Fig. 10a). Thus, APD yielded generally higher densities than
The reported shrinkage values depend on the assessment SCD, as presented in Fig. 10b.83
method. One of the ways consists in the measurement of the Li and co-workers164 reported another detailed observation of
initial volume of the mould,208,209 or allowing the gelation to the range of low % of bres. They synthesised silica aerogel
occur and measuring the volume of the wet gel,42,83 in composites from TEOS, with 0 to 1.5 volume% of sepiolite
comparison to the nal volume of the dried material; these reinforcing bres (2–10 mm length) dispersed in the sol, and
methodologies will express higher shrinkage values, since the dried under supercritical conditions. A small amount of bres
obtained values are cumulative values of ageing and drying (0.5 vol%) prevented part of the shrinkage, resulting in slightly
shrinkage. The other way consists of carrying out the assess- less dense materials (from 200 to 190 kg m3), in spite of the
ment aer the ageing step, expressing solely the shrinkage due mass addition; an increase of bre content led to a denser
to drying.57,210 Moreover, some authors report the linear material (up to 210 kg m3), since the density of sepiolite bres
shrinkage (usually in the diameter) and others report the (2.0 g cm3)164 is much higher than the aerogel density.
volume shrinkage, the latter leading to signicantly higher A similar nding was published by Li et al.,37 regarding silica
values. Oen, the adopted method is not clearly disclosed. aerogel composites reinforced with attapulgite bres (a crys-
As reported by Markevicius et al.,83 during the ageing process talline hydrated magnesium aluminum silicate). TEOS was the
of a pure silica gel, the volume shrinkage (occurring due to the used precursor and a surface treatment was performed with
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Fig. 10 Silica aerogels’ (a) cumulative volume shrinkage (during ageing

and drying) and the corresponding (b) final density as a function of
Tencel® fibres’ weight fraction, for ambient pressure and supercritical
drying (aerogels without fibres collapsed during ambient pressure
drying) (reprinted with permission from Springer Nature: J. Mater. Sci.,
from ref. 83, copyright 2016).
trimethylchlorosilane (TMCS/ethanol/n-hexane solution),

before APD of composites under a multistep temperature
gradient. The mass of bres varied from 0 to 20%, with linear
shrinkage gradually diminishing from 32.3 to 10.2%, as depic-
ted in Fig. 11a. Bulk density signicantly decreased from 188 to
163 kg m3 aer adding 1 wt% bres, and then gradually rose
until 192 kg m3. As claimed by the authors, bres induced the
aerogel matrix to withstand drying stresses, providing lighter
materials with a precise addition of bres.37 It is worth high- Fig. 11 Density and shrinkage of silica aerogel composites as a func-
lighting the higher level of % shrinkage in APD compared to tion of reinforcement with (a) attapulgite fibres, APD (after surface
SCD, despite the effectiveness of hydrophobic surface treat- treatment) (reprinted with permission from Springer Nature: J. Sol-Gel
Sci. Technol., adapted from ref. 37, copyright 2017); (b) silica fibres,
ments applied to the composites before APD.
APD (after two-step surface modification) (adapted and reprinted from
In opposition to the monotonic decrease of shrinkage as ref. 57, copyright 2015, with permission from Elsevier). All sketches
a function of bre content, Shao and colleagues57 reported were drawn from the published data, with the lines as a guide for the
a different pattern, as depicted in Fig. 11b, regarding sodium eye, and each arrow pointing to the respective vertical axis.
silicate/MTES (1/0.3) composites reinforced with silica bres
(from 3.5 to 17.5 wt%), with a two-step MTES-TMCS modica-
tion. The APD dried composites achieved null volume shrinkage supercritically dried. They generally concluded that the higher the
at 7 wt% bre reinforcement. However, the optimal perfor- bre fraction, the lower the density of aerogel composites. This
mance (a balance between insulation and mechanical behav- was attributed to the support of the matrix provided by the bres,
iour) was achieved at 10.5 wt% (vide Table 3). With further bre which leads to a decrease of total shrinkage.47
addition, shrinkage increased and reached 24%, similar to the The observations reported by Gao et al.213 in a subsequent
native, although two-step modied, silica aerogel. The authors study are in line with those of Parmenter and Milstein.47 The
attributed the fact to an incomplete surface modication aerogel composites were TEOS-based, reinforced with ceramic
caused by an excess of bres that caused the composite bres (mainly composed of SiO2 and Na2O) and supercritically
densication.57 dried in ethanol. The fraction of bres varied from 0 to 11.5
Parmenter and Milstein47 reported a different tendency when volume%, leading, respectively, to a variation of the composite
compared to those presented before. Both the density and bulk density between 202 and 142 kg m3, accompanied by
shrinkage decreased along with the increase of bre content. a decrease in shrinkage in the z direction, achieving a value of
These authors, who rst studied the qualitative correlation only 0.6%.213
between bre reinforcement and the shrinkage behaviour of silica In spite of very different ndings, there are some notes that
aerogel composites, used TEOS as the precursor and a mixture of can be outlined:
ceramic bres (68% silica with 3 mm diameter, 20% alumina with (1) The bulk density of silica aerogel composites is related to
2–4 mm diameter and 12% aluminoborosilicate with 8 mm diam- the type and fraction of bres used for reinforcement;
eter, all with 1.27 cm length), and the mass percentage of the (2) As a rule of thumb, the volume shrinkage of silica aerogel
reinforcement material varied from 0 to 25%. The bres were composites generally decreases with the increase of bre
added to the silica-based solution, and the composites were content.
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3.5 Effect of bre content on the mechanical performance of nanobres, using a three-point exural compression test. The
silica aerogel composites mechanical strength of composites linearly grew up to 0.06 MPa
(the higher strength was recorded at a density of 74 kg m3, with
The porous nanostructure of silica aerogels can lead to a very
3 wt% nanobres), and then decreased monotonically due to
low compressive strength, a property that might be critical in
a higher fraction of polyaniline, corresponding to a higher
the case of load-bearing applications.186,214
density of composites. The authors conjectured that aer the
Mechanical compressive failures in silica aerogel composites
maximum strength, the subsequent decrease was caused by the
can occur through different mechanisms, such as buckling,
delamination, shear deformation and bre rupture. Buckling is numerous bres interfering with the interconnections between
the main cause of bre break-up, when the stress load is silica particles in the network. The best mechanical perfor-
mance of a polyaniline–silica composite aerogel was 200%

transmitted to the reinforcing bres, leading to their fracture.215
higher than that of the pure silica aerogel of the same density.
According to the work of Parmenter and Milstein,47 both the
They also reported that the polyaniline–silica aerogel compos-
bre content and the material density determine the compres-
ites supported 8500 times their own weight, in opposition to the
sive strength behaviour of reinforced composites. These nd-
5000–6500 times of the pure silica aerogel counterpart.68
ings are depicted in Fig. 12, in which part (a) refers to the lower
Apart from the fraction of reinforcement material, the drying
densities and part (b) refers to the higher densities. A small
amount of ceramic bre addition, such as 5 wt%, increased the technique also determines the mechanical performance of
elastic modulus relative to that of the pure aerogel, and this was aerogel composites, since it inuences the level of shrinkage
and the related density, as previously described. This was evi-
particularly noticeable in structures with higher density
denced by Jaxel and co-workers,42 using the 3 point-bending test
(Fig. 12b), resulting thus in stiffer aerogels. With further
performed on aerogel composites of silica–Tencel® (bres z 14
increase of the fraction of bres, the Young's modulus
mm diameter and 8 mm length). The bre volume fraction
decreased, and hence the composites exhibited a higher degree
varied from 0 to z2%; the samples were both ambient pressure
of exibility (Fig. 12a, at 10 wt%), which can be advantageous to
and supercritically dried, giving densities of 103 and z124 kg
overcome the inherent brittleness and difficult handling of
silica aerogels. m3, respectively, for the neat silica aerogel and the composite
Gao and co-workers213 extended the study of mechanical with the higher content of Tencel® bres. The exural results
are presented in Fig. 13a (there are no results for ambient
performance by measuring tensile, bending and compressive
pressure drying with 0% bre content, due to the loss of the
strengths as a function of bre content and density of silica aer-
monolithic shape during drying42). The supercritically dried
ogel composites reinforced with ceramic bres (synthesis condi-
composites displayed higher stiffness, expressed by the higher
tions and variables previously described). The mechanical
values of moduli and maximum stress, compared to the
strength increased up to 1.2–1.4 MPa with increasing mass of
ambient pressure dried composites, which showed higher
bres up to 9.4 volume%, and then decreased, in accordance with
the results described by Parmenter and Milstein47 for the aerogel exibility (Fig. 13a and b). The authors attributed this fact to the
composites with the highest fraction of reinforcing bres. gel’s partial fragmentation during APD. Under stress loading,
the fragmented parts are sustained by the bres that smoothly
Regarding the results of the different mechanical strength
move into new rearrangements, while pure silica aerogels tend
tests as a function of density, Gao et al.213 reported an almost
to break completely.42
linear relationship between tensile/bending/compressive
Liao and colleagues119 and Hou and co-workers186 reported
strengths and density.
similar outcomes, summarised in Fig. 13c and d for: (c) a TEOS-
Boday and colleagues68 reported a similar trend for silica
based silica aerogel, reinforced with aligned glass bres (added
aerogel composites reinforced with organic polyaniline
to sol in layers perpendicularly oriented), modied by a TMCS/
Fig. 12 Stress–strain curves of silica aerogels under compressive load for various degrees of fibre reinforcement and aerogel composites’ final
densities (adapted and reprinted from ref. 47, copyright 1998, with permission from Elsevier).
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Fig. 13 Mechanical properties of silica aerogel composites: (a) flexural modulus and (b) maximum stress for supercritically dried and ambient
pressure dried silica aerogel composites reinforced with Tencel®, as a function of fibre volume (adapted and reprinted from ref. 42, copyright
2017, with permission from Elsevier); (c and d) compressive strength and bulk density of silica aerogel composites as a function of fibre weight
fraction, with related particularities inscribed (both drawn from the published data, (c) reprinted with permission from Springer Nature: J. Sol-Gel
Sci. Technol., adapted from ref. 119, copyright 2012; and (d) adapted from ref. 186, copyright 2018, with permission from Elsevier).
n-hexane solution and subjected to APD;119 (d) a composite increases almost linearly,37,164 as shown in the two examples of
developed from a mixture of precursors, TEOS and zirconium Fig. 14.
oxychloride, reinforced with dispersed ZrO2 bres added to the Other systems of silica aerogels with alumina, silica or
ZrO2–SiO2 solution, and subjected to SCD.186 As depicted in silicon carbide bres were reviewed and explained by Lee &
Fig. 13c, the increase of reinforcement material fraction, from Cunnington.177 According to their study, a low content of bres,
0 to 9 wt% glass bres, resulted in an increase of compressive with residual contact between them, has a negligible effect on
strength of the composites, from 0.72 MPa to 21.03 MPa (almost the solid heat conduction of the composites.177
30-fold), while the bulk density increased from 115 to 227 kg Liao and co-workers119 studied the effect of the fraction
m3 (less than 2-fold).119 The silica–zirconia composites rein- content of aligned glass bres (5–20 mm diameter) on the
forced with zirconia bres exhibited a positive and almost linear thermal conductivity of silica aerogel composites. Four layers of
correlation of bulk density and compressive strength with bres were alternately deposited in perpendicular directions
bre wt%, between 0 and z10 wt% (Fig. 13d). Beyond that and permeated with silica sol. The content of glass bres was 1,
point, the mechanical strength decreases with the addition of 4.2, 7 and 9 wt%. The increasing mass of bres led to different
bre mass. Hou et al.186 explained these results through an thermal performance behaviour: from 1 to 4.2 wt%, there was
excess of bres that led to clusters (non-homogeneous disper- almost no increase in thermal conductivity, attributed to a low
sion), which favoured bre slip off under stress load and the contact between bres, separated by the aerogel in-between;
composite failure.186 a further increase in the bre content, from 4.2 to 7 wt%,
The mechanical response of silica aerogel composites engi- increases the mutual contact between bres due to the nearest
neered for insulation at high/extreme temperature must fulll adjacent layers of glass bres, and thermal conductivity rises
two important requisites: (i) the ability to maintain thermal from 26 to 32 mW m1 K1, until full contact of bres; above
performance when subjected to a load; (ii) displaying the 7 wt% bres, the thermal conductivity increases only slightly.119
necessary degree of elasticity under that load.216 Lu and colleagues135 evaluated the thermal conductivity
The loss of integrity of silica aerogel composites under stress using different patterns between adjacent SiC bres embedded
load is oen the main factor of degradation of their insulation
performance due to induced cracks.216,217
3.6 Effect of bre content on the thermal conductivity of

silica aerogel composites
The fraction of bres reinforcing silica aerogel composites
dictates their thermal conductivity, which can also be inu-
enced by the type of bre.85,177 The trend observed for density in
the silica–sepiolite and silica–attapulgite composites (Section
3.4) is similar to the trend of thermal conductivity: a small
fraction of bres decreased the thermal conductivity relatively
to that of the neat aerogel, while for a higher amount of bres Fig. 14 Influence of fibre amount on the thermal conductivity of silica
aerogel composites: (a) volume% of sepiolite fibres (reprinted with
the thermal conductivity increases. In fact, higher porosity
permission from Springer Nature: J. Sol-Gel Sci. Technol., from ref.
prevailed over a small mass addition of the inorganic bres, and 164, copyright 2013); (b) wt% of attapulgite fibres (reprinted with
thermal conductivity decreases due to the increase of voids; but, permission from Springer Nature: J. Sol-Gel Sci. Technol., from ref. 37,
by increasing the amount of bres, thermal conductivity copyright 2017).
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in a silica aerogel. They assessed three possibilities: (i) strong In the aforementioned development of Markevicius and
contact, for effective contact between bres; (ii) non-ideal colleagues,83 cellulosic bres (Tencel®, 10 mm diameter and
contact, with air and cracks between bres; and (iii) ideal 2 mm length) were added to a silica sol at concentrations of 1,
contact, when the space around each bre was lled by the 1.5, 2 and 3 wt% (corresponding to 10, 15, 18 and 25 wt% of the
aerogel. The results are shown in Fig. 15a. The ideal contact dried composite). The inuence of APD vs. CO2 SCD on the
leads to the lowest thermal conductivity, suggesting that with insulation performance of composites was also studied. The
lower bre fraction (with reduced probability of mutual contact) thermal conductivity of cellulosic bres is higher than that of
better insulation properties can be achieved.135 the silica aerogel structure, ranging from 0.72–5.7 W m1 K1
Dissimilar achievements are also reported in the literature. in cellulose nanocrystals, to lower values of ca. 0.22–0.53 W m1
Jiang and colleagues85 developed a silica aerogel composite, K1 in more organized man-made materials, such as cellulosic
reinforced with a microglass bre mat (2–4 mm diameter), with lms.219 Therefore, it is expected that the addition of cellulosic
a volume content of 4.5, 6.8, or 9.1%. The results are depicted in bres, while providing reinforcement of silica aerogels, would
Fig. 15b: the higher the volume of bres, the lower the thermal have a detrimental effect on their insulation features. In fact,
conductivity of the composite. According to the authors, the the thermal conductivity of composites slightly increased with
results can be understood in light of the small diameter of the the increase in the fraction of bres, as depicted in Fig. 16.
glass bres, and the consequent high specic surface area. The SCD composites showed z7% better performance in
Thus, the higher the bre content, the higher the ability to terms of insulation, attributed to the reduced shrinkage, thus
suppress the radiative heat conduction. This is supported by the lower density, compared to the APD composites.83
slope of thermal conductivity curves with increasing tempera- This group of researchers also assessed the insulation
ture: the composite with higher bre content exhibited the properties of other cellulosic bres compared to those of
lower slope.88 Tencel®, namely ax and recycled paper bres, all with 25 wt%
In Fig. 15c, corresponding to the work of Yuan et al.,218 the embedded bres in the silica matrix. According to their results
trend is the opposite: the higher the content of glass bres, the the silica–Tencel® composites performed around 13–14%
lower the insulation performance of the silica aerogel better.83 Yet, all the composites still exhibit values below the
composite, which was attributed to an eventual higher thermal conductivity of free air under standard conditions (25
connection between bres, enabling the creation of new paths mW m1 K1), with insulation performance similar to that of
for heat leaking,218 but it can also be related to the higher super-insulating materials. This was attributed to the meso-
diameter of glass bres, which was 12 mm, while Jiang and co- porous structure of the gel, not signicantly damaged during
workers85 used bres with a smaller diameter (2–4 mm). drying.
The different trends of thermal conductivity as a function of The incorporation of cotton bres also increases the
bre fraction, by comparing the composites developed by Jiang conductivity of silica aerogels, in accordance with the work of
et al.,85 Liao et al.119 and Yuan et al.,218 are in accordance with the Rezaei and Moghaddas.192 Even though the structural strength
degree of contact between bres in the structures; when of composites increased, in order to maintain their thermal
disposed in layers, the stronger contact between bres poten- conductivity below the thermal conductivity of free air, the
tiates an increase of conductivity.135 Nonetheless, all the cotton bre addition was limited to a maximum content of
composites provided better insulation features than commer- 60 wt% of the dried aerogel, according to the authors. These
cial bre glass insulators, whose typical values of thermal composites were obtained from a water glass precursor and
conductivity are around 40 mW m1 K1,83 as shown in Fig. 4. APD, aer surface modication with TMCS in hexane.192
Fig. 15 Thermal conductivity of silica aerogel composites: (a) effect of contact patterns of the reinforcement with SiC fibres (diameter between 2
and 5 mm), measured at 300 K and ambient pressure (adapted and reprinted from ref. 135, copyright 2011, with permission from Elsevier); (b and
c) trends of thermal conductivity as a function of fibre content: (b) volume fraction of glass fibres, with 2–4 mm diameter (reprinted with
permission from Springer Nature: J. Sol-Gel Sci. Technol., from ref. 85, copyright 2017); (c) mass fraction of glass fibres, 12 mm diameter (adapted
and reprinted from ref. 218, copyright 2012, with permission from Elsevier).
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Additionally to the size of pores, their relative volume is also

a key factor of insulation performance, as demonstrated by
Shao et al.:57 while the pristine silica aerogel (rb ¼ 125 kg m3,
APD), with a mesopore volume of 96.6% displayed a thermal
conductivity of 20 mW m1 K1, aer the addition of 17.5 wt%
silica bres (rb ¼ 146 kg m3, APD) the mesopore volume
lowered to 77.7% and the thermal conductivity increased to 30
mW m1 K1 (even so, a very good result was achieved with
composites).
3.6.1 Opacied silica aerogels: bres as a shield for radia-

tive conductivity. The before mentioned eqn (5) highlights the
inuence of environment temperature on the radiative thermal
conductivity of monolithic silica aerogels, which can be domi-
nant over the other two components of thermal
conductivity.144,177,220
Fig. 16 Thermal conductivity of silica aerogel composites with When exposed to temperatures above 600–700 C, the
Tencel® fibres, obtained by APD and CO2 SCD (no results are shown structure of native silica aerogels deteriorates due to viscous
for the APD-pure aerogel due to its collapse during drying) (reprinted
with permission from Springer Nature: J. Mater. Sci., from ref. 83,
sintering. This phenomenon can lead to a partial loss of the
copyright 2016). porous morphology and subsequent densication, imposing
restrictions on their applicability as thermal barriers.221,222 On
the other hand, the spectral mass attenuation coefficient of
In the development of pectin–silica composite aerogels, by native silica aerogels is less than 10 m2 kg1 for wavelengths
dissolving pectin in water-glass-derived silicic acid solution, the around 3–5 mm, while in the hybrid silica aerogel, heat mitiga-
as-prepared high methoxy content pectin nanobres remained tion in that IR wavelength range can be increased around 100
interpenetrated within the silica matrix.155 The aerogels syn- times,223 as shown in Fig. 17.
thesised at pH 1.5, 3 and 5 and reinforced with 5, 10 and 20 wt% Actually, an effective way to improve silica aerogels’ effi-
pectin nanobres exhibited improved insulation properties ciency for high temperature applications is the attenuation of
when compared to the pristine aerogel counterpart. While the radiative heat transfer, either by scattering or absorption, which
pectin–silica composites displayed thermal conductivity values can be accomplished with the embedment of infrared opaci-
between 14 and 17 mW m1 K1, the thermal conductivity of the ers, such as soot, TiO2 particles or inorganic bres.133,177,224,225
native silica aerogel was 17.4 mW m1 K1.155 One possible Fig. 17a illustrates the effectiveness of a carbon-based additive
reason for these results may be the smaller dimensions of pores (soot) in enhancing IR shorter wavelength absorption. Soot is an
in the hybrid aerogels,31 since the diameter of pores in the efficient opacier, with a mean spectral mass attenuation
composites was z11 nm, while it was around 14 nm in the coefficient of 600 m2 kg1,226 as described in Table 5, signi-
native silica aerogel, on average.155 As revealed by Zhao et al.,155 cantly higher than the values of the other typical opaciers, also
the composite synthesised at the smaller pH and with a small presented therein. However, in spite of196,197 its broad-band
load of pectin bres exhibited the lowest thermal conductivity: absorption, the carbon black opacier becomes unstable
14.2 mW m1 K1. above 573 K,135 and is prone to oxidation reactions in high
temperature environments.133
Fig. 17 Spectral mass attenuation coefficient of opacifiers used in silica aerogels: (a) carbon-based, as a function of wavelength (reprinted and
adapted from ref. 137, copyright 1992, with permission from Elsevier); (b) spectral mass attenuation coefficient of an opacified silica aerogel with
TiO2 particles and ceramic fibres (adapted and reprinted from ref. 133, copyright 1995, with permission from Elsevier); (c) comparative
performance of carbon black and other commonly used aerogel opacifiers, as a function of temperature (adapted and reprinted from ref. 229,
copyright 2016, with permission from Elsevier).
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Table 5 Spectral mass attenuation coefficients, e, for fibres and opacifiers in the wavelength range 1–50 mm
Particle or bre e
Material diameter (mm) (m2 kg1) References
5% Fe3O4 in fumed silica 2 40 Fricke et al.226

5% TiO2 in fumed silica 2.5 40 Fricke et al.226
10% TiO2 in SiO2 aerogel (rb ¼ 170 kg m3) 3.5 14 Kuhn et al.227
30% TiO2 in SiO2 aerogel (rb ¼ 220 kg m3) 3.5 66 Kuhn et al.227
Soot <0.1 600 Fricke et al.226
Glass bre 5 50 Fricke et al.226
SiO2 bre 10 30 Fricke et al.226

AlO3 bre 4 50 Fricke et al.226
SiC bre 1.5 160 Wang et al.228
TiO2 combined with inorganic bres, such as alumina or 3.7 Inuence of bre morphology/size
silica, is oen used as an opacier in silica aerogel compos- The physical adhesion between the silica phase and the rein-
ites,227,228 with diverse applications, such as in aerospace engi-
forcing brous matrices tends to be improved with the rough-
neering, high temperature energy storage or even solar energy
ness of bres' surface.232 Other relevant parameters of bres for
devices.224 As the attenuation coefficient of the native silica
the nal properties of aerogel composites are mentioned below.
aerogel decreases with rising temperature and is much smaller
3.7.1 Length-to-diameter ratio. The skeleton structure of
than that of inorganic bres, the silica aerogel with embedded
monolithic silica aerogels is formed according to the percola-
inorganic bres can be quite effective in suppressing the radi-
tion theory: each individual chain constituting the aerogel
ative heat.137
lattice grows aer addition of new particles, randomly occu-
Wang and colleagues133 pioneered these studies, by mixing pying available sites, under a certain probability, p. If p is small,
ceramic bres with TiO2 particles (mean diameter of 3.5 mm).
only nite clusters are formed; when p exceeds the percolation
The strengthened composites were synthesised from TMOS,
threshold, a continuous 3D assembly occurs, along with the
and had higher absorption of the IR shortest wavelength (see
individual chains.233 The theoretical volume fraction of bres
Fig. 17b), widening their applicability for high temperature
(or particles) above which a continuous network is formed is
environments. According to their studies on how doped silica
designated as the percolation concentration.42
aerogels (with 30% TiO2 + 3 wt% ceramic bres, rb as 260 kg
There is a correlation between length-to-diameter ratio of
m3) performed in an increasing temperature environment, the
bres and the value of percolation concentration, which can be
total thermal conductivity was 38 mW m1 K1 at 800 K, while approximately estimated as being the inverse value of length-to-
that value for a conventional insulating material, such as an
diameter ratio. As an example, to obtain monolithic aerogels
alumina-fused brick, is around 100 mW m1 K1.133 Yet, the
dried at ambient pressure, the minimum amount of cellulosic
thermal stability of SiC bres leads to improved performance
bres with a length of 2 mm and diameter of 14 mm has to be
compared to TiO2 or zirconium bres, in a range above the
z0.7% volume. However, for easy handling of materials, as well
service temperature of carbon opaciers commonly used, with
the diameter at an optimal size,229 as illustrated in Fig. 17c.
Several research studies revealed similar trends regarding
the thermal conductivity at high temperature, such as the
examples depicted in Fig. 18. Silica aerogels supercritically
dried and strengthened with 5% volume of amorphous SiO2
glass bres displayed low radiative thermal conductivity with
increasing temperature up to 1300 K, compared to the pure
silica aerogel,178 depicted in Fig. 18a.
Another aerogel composite with 10 wt% mullite bres
(3Al2O3$2SiO2), synthesised in one step from sodium silicate
precursors, modied by trimethylchlorosilane and dried at
ambient pressure, when exposed to temperature above 300 C
showed better thermal insulation than the pristine aerogel.230
This last study was conducted below the sintering temperature
of native silica aerogels (Fig. 18b). By selecting a suitable Fig. 18 Effect of increasing environmental temperature on the
morphology and content, the addition of inorganic bres is thermal conductivity of an opacified silica aerogel in comparison to
a proven technique to suppress thermal radiation, therefore the native silica aerogel: (a) aerogel composites with 5 volume% of
enabling the decrease of the total thermal conductivity of silica amorphous SiO2 (adapted and reprinted from ref. 178, copyright 2012,
with permission from Elsevier), and (b) composites filled with 10 wt%
aerogels in high temperature environments.150 Enhanced mullite fibres (adapted from ref. 230, copyright 2016, with permission
results can be achieved with bres of small diameters.85,231 from Atlantis Press).
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However, an excessive length of the bres can be detrimental

to aerogel's mechanical performance, as explained by Bun-
sell:236 as the intrinsic material defects randomly occur at
individual units or linkages of the bres, the bigger its length,
the higher the probability of a weakened bre.236
The length of bres can also inuence the thermal conduc-
tivity of silica aerogel composites. According to a study involving
cellulosic bres with 2, 6, 8 and 12 mm length, the maximum
insulation performance was recorded in the composites with 6
and 8 mm bre length. The researchers hypothesised that

higher dimensions of bres might increase their mutual
contact and favour the solid thermal conductivity. On the other
Fig. 19 Effect of fibre length-to-diameter ratio on the mechanical
hand, short length bres lead to a higher level of densication
properties of silica aerogel composites (reprinted from ref. 235,
copyright 2015, with permission from Elsevier). during ambient pressure drying.42
3.7.3 Diameter. Some examples had been presented
already in this review highlighting the inuence of bre diam-
eter on the nal properties of the aerogel composites.
as to minimize collapse or shrinkage during drying, the value of
Depending on the type of bre, there is an optimum diameter at
% volume of those bres must be at least twice the value of the
which the maximum spectral mass attenuation coefficient is
percolation concentration.42
achieved229 (vide Fig. 17c). This is a noteworthy variable in the
The length-to-diameter ratio of bres also inuences the
conception of thermal barriers for high temperature environ-
mechanical behaviour of the composites.234 According to a study
ments. Silica based bres are oen used in those materials.
carried out by Lu and co-workers,235 the tensile strength of a silica
According to several studies, silicon carbide bres with
aerogel, reinforced with 7% volume of ceramic bres, increased
diameters around 4–6 mm provide the best insulation properties
linearly with their increasing ratio, from less than 1.1 MPa (at
when embedded in hybrid silica aerogels.27,150,229 Tang and
a ratio of 500) to more than 1.4 MPa with a bre ratio of 3500. For
colleagues229 determined more specically the optimal SiC
higher ratios, the tensile strength decreased slightly (Fig. 19).
diameter concerning the intended operating temperature
3.7.2 Length. Monolithic ambient pressure dried silica
(Fig. 20a). Also, the diameter of amorphous glass bres, in order
aerogels can be synthesised without additional chemical treat-
to minimize the thermal conductivity for a given service
ments, as long as bres are embedded, in order to prevent their
temperature, was assessed by Zhao and co-workers178 and is
collapse, as aforementioned. Notwithstanding, there is
presented in Fig. 20b. According to their work, silica aerogels
a minimum bre length to be able to endure the capillary
reinforced with bres with diameters of 4, 6 and 8 mm displayed
stresses and to sustain the structure. According to the work of
the highest insulation performance at 1300 K. The study was
Ślosarczyk,232 in spite of the huge amount of carbon nanobres
carried out with composites of density of 110 kg m3 and 94%
with a length of 20 nm (15 vol%), the aerogel composites
porosity, with 5% volume of bres. Tang and co-workers229 also
collapsed into fragmented pieces under ambient pressure
assessed the optimal reinforcing bre diameter in order to yield
drying. In order to obtain monolithic samples, the bre length
the optimal density of silica aerogel composites, leading to the
had to be around 700 mm.232 In fact, longer ceramic bres
best insulation performance and covering a broad temperature
provided better reinforcement and improved the mechanical
range. The lightest insulation materials were made with SiC
performance of the silica aerogel composites.235
bres – Fig. 20c. Apart from carbon black, in the lower
Fig. 20 Fibre diameter for optimal insulation performance as a function of temperature: (a) silicon carbide (reprinted from ref. 229, copyright
2016, with permission from Elsevier); (b) amorphous glass fibres (adapted and reprinted from ref. 178, copyright 2012, with permission from
Elsevier); (c) optimal density of silica aerogel composites for a wide range of temperature, reinforced with fibres with optimal diameter (reprinted
from ref. 229, copyright 2016, with permission from Elsevier).
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temperature range, aerogel composites embedded with SiC the highest value. In order to improve the mechanical proper-
bres displayed the lower thermal conductivity. ties, mainly the shear strength, the incorporation of bres
With regard to mechanical performance, toughness and randomly oriented in space, along with other bres in the plane
exibility are the features to be assessed during selection of the normal to the heat ux, might be an effective solution, despite
reinforcement bres. Bunsell236 related the bre exibility with the increase of the thermal conductivity, especially for high
a function of the reciprocal of the diameter to the fourth power, temperature applications.177
that is to say, the exibility of a bre can be increased 16 times In fact, the total thermal conductivity of silica aerogel
by halving its diameter, as presented in eqn (7): composites can be adjusted accordingly to the inclination angle
of embedded bres, either in low or high temperature envi-
64Fl 3
Fibre flexibility ¼ (7) ronments. Zhao and co-workers178 reported the inuence of the
3EpD4
orientation of glass bres, by varying the heat ux incident
where Fl is the bending moment produced by the applied force angle, 4, between 0 and 40 (4 ¼ 0 when bres are perpen-
F at the free end of the length l, E is the bre stiffness or Young's dicular relative to the heat direction): the thermal conductivity
modulus and D is the bre diameter. of aerogel composites increased from 20 to 55 mW m1 K1, at
Such a relationship emphasises the prevalent trend of 250 K, and from 80 to 195 mW m1 K1, at 1250 K, as illustrated
ceramic bres in silica aerogel reinforcement, since stiff mate- in Fig. 22a. Lu and co-workers135 corroborated and com-
rials can still be exible materials in the form of ne bres. plemented those ndings by evaluating the effect of increasing
3.7.4 Curvature. The architecture of bres in the three- the volume fraction of SiC bres, oriented in the planes
dimensional space or in a plane greatly inuences the perpendicular and parallel to the heat ux, on the thermal
mechanical performance of silica aerogel composites, namely conductivity of aerogel composites, with the perpendicular
the tensile strength and Young's modulus. As depicted in array being the best option for thermal insulation (Fig. 22b).
Fig. 21, the less the curvature of the bres, the highest is the Moreover, the difference in the plotted curves of the total
strength of the composites, since the curved shape inhibits the thermal conductivity between the planes (the perpendicular
loading stress to be transferred from the matrix to the bres, and the parallel array of bres) gradually increased along with
diminishing their role in reinforcement.235 It should be noted the volume of bres, due to the worst insulating properties of
that as the curvature of the bres increases, there is an SiC bres compared to the pristine silica aerogel matrix.135
improvement in the accuracy of the results. Fibre orientation also inuences the mechanical properties
of silica aerogel composites. The multilayer effect on silica
3.8 Inuence of bre orientation aerogel composites was studied by Wu et al.,120 using different
The absorption and scattering characteristics of each bre are combinations of glass bre alignment (5–20 mm diameter and
related to the angle of incidence, dened between the incident 3% volume). They were deposited longitudinally (L) and trans-
radiation and the plane normal to the longitudinal axis of the versally (T), in six different designs (LLLL, LTLL, LLTT, LTLT,
bre.177,237 LTTL, and LTTT), added sequentially and permeated with
Apart from the optical properties and volume fraction, bre a silica sol, as depicted in Fig. 23. All the bre layers in the same
orientation is an important parameter for the thermal direction (LLLL design) imparted to the composite the highest
conductivity of aerogel composites. According to the studies of compressive strength, 3.70 MPa at 50% strain, more than two-
Lee & Cunnington,177 25 wt% SiC bres with 15 mm diameter
randomly oriented in a plane normal to the heat ux imparted
the lowest conductivity to a silica aerogel composite (rb ¼ 105
kg m3), while the bres randomly oriented in space imparted
Fig. 22 Effect of fibre orientation on the thermal conductivity of silica

aerogel composites: (a) thermal conductivity as a function of
increasing temperature and varying the incident angle (4) of heat flux
in aerogel composites with amorphous glass fibres (adapted and
reprinted from ref. 178, copyright 2012, with permission from Elsevier);
Fig. 21 Effect of the curvature of ceramic fibres on the tensile prop- (b) effect of SiC fibre volume fraction and preferential orientation on
erties of silica aerogel composites (reprinted from ref. 235, copyright the total thermal conductivity, measured at 300 K (adapted and
2015, with permission from Elsevier). reprinted from ref. 135, copyright 2011, with permission from Elsevier).
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4 Applications of fibre–silica aerogel

composites
The most important applications of bre-reinforced silica aer-
ogel composites are presented here.
Fig. 23 Two examples of arrangement (LLLL and LTLT) of the six

possible combination layers of aligned glass fibres permeated with
4.1 Thermal insulation
a sol for the preparation of silica aerogel composites (reproduced and According to our survey, thermal insulation is the preferred
adapted from ref. 120, with permission from Taylor & Francis Ltd, application of silica aerogel composites. Heat barriers must be
http://www.tandfonline.com, copyright 2014).
highly porous materials, in order to display low thermal
conductivity. Silica aerogel composites fulll such a requisite.
Different brous matrices were/are used for aerogel rein-
fold relatively to the composite with alternate directions of bre
forcement, which might enhance their applicability as thermal
layers (LTLT), which withstood a load of 1.71 MPa. According to
insulation barriers: glass bres; ceramic bres, such as xonot-
the authors, the perpendicular direction alignment between two
lite,136 Cerachrome®, Saffil® or Q-Fiber® Felt;3 aramid bres,
adjacent layers might be prone to create weakened stress
such as Nomex®,3 or Kevlar®;121,167 zirconium dioxide;186 poly-
points.120
propylene;127 cellulosic nanobres;238 cotton;192 and even ax.83
As a conclusion of this topic, it can be stated that the
Table 6 describes the relevant features of silica aerogel
thermal and mechanical behaviour of bre-reinforced silica
composites, when they have been envisioned for insulation
aerogels can be tailored to the intended application by design
purposes in room temperature environments. Some of the re-
of bre alignment, either to achieve optimal insulation
ported values therein were obtained from the graphical results
features177 or improved response in mechanical
reported in the cited literature. The presentation of the studies
performance.119,120
is ordered according to the drying technique used (SCD, freeze-
drying (FD) or APD). Regarding the thermal conductivity results,
Table 6 Summary of the main properties of fibre–silica aerogel composites developed for insulation purposes at room temperatures
Porosity Specic surface Thermal conductivity

Fibres Drying technique rb (kg m3) (%) area (m2 g1) (mW m1 K1) References
Pectin SCD 130 92 827 14.2 Zhao et al.155

Cellulose nanobers SCD 142 — 525 15.3 Hayase et al.31
Sepiolite SCD 190 3.16a 950 19.7 Li et al.164
Cellulose nanobres FD/SCDb 146 94 454 17.5 Zhao et al.241
Glass FD 174 1.80a 871 24.8 Zhou et al.242
Tencel® (cellulosics) APD 109 — 600–700 16.0 Jaxel et al.42
Cotton APD 125 — — 17.0 Rezaei et al.192
Aramid APD 142 84 973 23.6 Li et al.121
Glass APD 142 88 964 23.2 Li et al.168
Carbon APD 153 1.44a 538 26.1 Ślosarczyk232
a
The value refers to the pore volume (cm3 g1). b
FD for the cellulose nanobre scaffold, and SCD for the silica–nanobre composite.
Table 7 Some properties of fibre–silica aerogel/xerogel composites applicable in high temperature environments
Upper limit of Thermal Mechanical

rb service temperature conductivity strength
Fibre content (kg m3) ( C) (mW m1 K1) (MPa) Special remarks References
Glass (20 wt%) + TiO2 (20 wt%) 410 700 30 0.8a Silica aerogel powder, Yuan et al.218
pressed at 1.5 MPa
Glass (9.1 volume%) 129 650 22 1.4b Fibre batting; APD Jiang et al.85
Mullite (20 wt%) z115 500 39 z12.5c Mechanical Liu et al.230
strength > z4-fold than
that of the native aerogel; APD
Mullite (z70 wt%) 450 1200 182 1.05a ZrO2–SiO2 aerogel; pre-form of He et al.243
bound bres,
with 89% porosity; SCD
a
Compressive strength. b Bending strength. c 3 point bending storage modulus.
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it is generally perceived that a better insulation performance is pollutants from aqueous streams, or deionization and electro-
accomplished by SCD, mainly related to the residual shrinkage chemical purication of brackish water (#5000 ppm). Aer
during drying, thus yielding composites with higher porosity. polarization of the operating cell, through which the salty
Good results were as well achieved aer freeze-drying. Never- solution ows, the imposed eld deects anions and cations,
theless, very good results are disclosed with APD drying, which are then electro-sorbed by carbon aerogel electrodes,
revealing the benecial effect of bre embedment on inhibiting with surface areas increased up to 2600 m2 g1.240
the loss of porosity during drying. Since then, the application of aerogels in environmental
There is also a correlation between thermal conductivity and remediation has been an increasing practice,10,74 and the trend
bulk density, as mentioned before: the insulation feature tends is also valid for silica aerogels with embedded bres.244,245 The
to deteriorate with increasing density, which might be attrib- chemical versatility of silica aerogels (along with their rough
uted to a higher fraction of bres. surface and huge surface area) allows them to be tailored for
Silica aerogel composites with inorganic bres, developed specic adsorption purposes. For example, the graing of non-
under appropriate synthesis conditions (such as low pH, longer polar groups decreases their surface energy, enhancing the
ageing times or surface modication), can inhibit extreme interactions of aerogels with other non-polar species, such as
temperature heat transfer. These materials can be applied, for polluting oils,246–248 as seen in Fig. 24.
example, for protecting building steel frames during res, thus That induced hydrophobicity enhances the buoyancy of
preventing the structure from soening and collapse, as aerogels in polluted waters, unlike several organic and natural
described by Motahari & Abolghasemi.208 sorbents, which are oen used due to their known efficiency
Along with the effective thermal insulation at high temper- (such as low grade cotton, kapok or rice straw).249
ature, high-tech applications also require efficient mechanical In addition, the incorporation of small amounts of bres in
performance,135,179 which is affected by the skeletal rearrange- aerogels improves their mechanical performance, allowing the
ment of aerogels induced by increasing temperature (the repeatability of adsorption and desorption processes.245
aforementioned aerogel's sintering). This phenomenon may Table 8 summarises some of the available results on removal
result, for example, in a partial reduction of the Young's of organic pollutants from the environment, performed by silica
modulus.212 aerogel composites with quite different brous materials.
Table 7 highlights some of the properties of aerogel Superhydrophobic materials were successfully developed,
composites developed for high temperature environments. aer a surface modication with TMCS in n-hexane: (i) a poly-
As previously mentioned, the compressive strength of acrylonitrile–silica aerogel displayed a contact angle of 169 (6 h
unmodied silica aerogels (with a density of 96 kg m3) is silylation treatment, at 40 C);245 (ii) an attapulgite–silica aerogel
approximately 0.04 MPa.188 The mechanical performance of composite exhibited a contact angle of 153 (soaked for 36 h for
silica aerogel composites, even when subjected to high silylation treatment, at 60 C).244 Additionally, Wei et al.250
temperatures, remained signicantly higher, this being evaluated the comparative performance of different bres in
a fundamental requisite for such application elds. Also, the terms of their chemical structure, concluding that the adsorp-
bending strength of native silica aerogels with a density of tion capacity for organic pollutants is around 6 to 8 times the
z100 kg m3 is around 1 MPa,211 which is below that observed composite weight.250 Slightly better performance was achieved
by Jiang et al.85 and Liu et al.230 with composites reinforced with hydrophobic bres, as ex-
As reported by Jiang et al.,85 aer reinforcement with glass pected for non-polar pollutants.
bres, and in spite of the temperature (650 C), silica compos- In light of the results, bre-reinforced silica aerogels are
ites can endure high mechanical strength, still being a superior remarkable adsorbent materials. Moreover, Shi et al.245 stated
insulating material, with a thermal conductivity of 22 mW m1 that diesel oil adsorption/desorption processes could be
K1, which is below the thermal conductivity of free air under repeated at least 100 times.
standard conditions.
4.3 Acoustic insulation

4.2 Adsorption of harmful compounds
Noise pollution has become a critical matter in people's daily
Farmer239 rst reported the use of aerogels (carbon-based) in life, a problem demanding more effective solutions in the
a pioneering technique for continuous removal of ionic prevention of health issues.251 Aerogel-based sound attenuation
barriers are among the related cutting edge technologies.252
Noise mitigation is dependent on material's thickness,253
interrelated with the wavelength: in order to attenuate a sound
wave of wavelength l, the thickness of each discrete insulation
layer must be at least l/2.169
Sound wavelength increases with decreasing frequency, and
hence, a low frequency range (100–2000 Hz) requires thicker
Fig. 24 Sorption of diesel oil by silica aerogels with 0.3 wt% poly-
insulation barriers,254 diminishing the available and useful
acrylonitrile fibres, within a minute of exposure (reproduced from ref. space, which can be particularly detrimental in conned spaces.
245, published by The Royal Society of Chemistry, copyright 2017). Consequently, aerogel composites are the best-suited materials
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Table 8 Applicability of fibre–silica aerogel composites in environmental remediation
Surface Sorption
Fibre for aerogel rb area Pore volume Pore Contact capacity
reinforcement (kg m3) (m2 g1) Porosity (%) (cm3 g1) diameter angle Adsorbate (g g1) References
Polyacrylonitrile 86 z230 95 5.56 5–20 mm 169 Diesel oil 9.6 Shi et al.245
Acetone >12
Nitrobenzene >13
Paraxylene >12
Tetrahydrofuran >13
N-Methyl-2-pyrrolidone 14.7
Toluene >9
N-Hexane >6
Vegetable oil >9
Attapulgite 550a 594 75 2.15 84.7 nm 153 Petroleum 5.0 Zhang et al.244
hydrocarbons
Polyester 625 805 68 1.09 — — Benzene >7 Wei et al.250
Toluene >6.5
Polypropylene 716 823 63 0.88 — — Benzene >8
Toluene >6.5
Lignin 678 805 65 0.96 — — Benzene >6
Toluene >6
Polyacrylonitrile 703 841 64 0.91 — — Benzene >6
Toluene >6.5
a
Apparent density.
for the insulation of low frequencies, due to their efficiency at reported by Groß and co-workers,70 although this value had
reduced thickness.169 been achieved aer aerogel's evacuation.
The porous nature of silica aerogels, which hinders heat In spite of the improvement of acoustic insulation with the
transfer, is also an ideal feature to achieve effective acoustic decrease of aerogels' density, their inherent fragility poses
insulation.4,5 The sound attenuation relies on the fraction of difficulties for most end applications.259 The incorporation of
energy loss, since the acoustic waves are successively trans- bres makes possible easy handling, allowing the applicability
ferred through the gas and solid phases, gradually reducing of lighter aerogels to be extended, while endowing the materials
their amplitude.255 with a higher degree of exibility. By using polyethylene tere-
The acoustic insulation provided by aerogels is a function of phthalate (PET) nonwoven fabric with 5 mm thickness and
several factors, related to the preparation procedures: material's a density of 37 kg m3, exible PET–silica aerogel insulation
density, interstitial gas pressure and their overall texture.255 For blankets were manufactured with two different methods: (1) by
example, surface roughness and larger pores are advantageous pouring the silica sol over the nonwoven bre mat before
features.256,257 This was demonstrated by Martin and gelation and (2) by dipping the brous mat into a dispersion of
colleagues,256 in their work on the development of silica aero- ethanol and hydrogel granules that were already aged.261 In the
gels by using polyethylene glycol (PEG) to control pore dimen- last method, the sol was allowed to gel and, aer gelation, it was
sions. Polymers are known to be used as porogen additives, subsequently broken into particles by ultrasonication, which
allowing controlled design of hierarchically porous materials.72 were then aged in an ethanol bath.261 The purpose of Oh
For example, by increasing the concentration of high molecular et al.'s261 work was to simplify aerogel production processes,
weight PEG in the sol, aerogels with higher pore dimensions mainly in terms of costs, since aerogel granulates can be used to
can be produced.72,256 The sound velocity across native aerogels build effective insulator systems,115,262 being less expensive than
was reported as 241.0 m s1, being reduced to 103.2 m s1 aer monolithic aerogels.262–264 The composites developed with the
PEG addition at a concentration of 10.2 mg L1.256 rst method were actually the most effective in acoustic insu-
Similar to the heat transport, there is a relationship between lation, especially at frequencies between 1000 and 6000 Hz. The
sound propagation and aerogel's density,65 according to eqn (8): analyses were performed in terms of sound absorption coeffi-
cient, described as the fraction of sound energy absorbed by
Vsound f rba, a z 1.0.1.4 (8) a material, with values ranging between 0 and 1 (1 – perfect
absorber). At frequencies of 2000 and 5000 Hz, the samples
The propagation speed of longitudinal sound waves through developed with method 2 (rb around 158 kg m3) displayed
native silica aerogels is typically 100 m s1, for densities around a value of z0.2, while in method 1 (composites at rb around 65
100 kg m3.258–260 In the case of extremely light aerogels, for kg m3) it was >0.4.261
instance with 5 kg m3, a sound velocity of 20 m s1 was
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An aerogel composite based on polyacrylonitrile and silica Conventional optical bres have thick walls, the cladding,
electrospun nanobres (with apparent density ¼ 9.6 kg m3), which has a smaller refractive index in comparison to the core.
developed under freeze-drying and cross-linked with heat So, light is successively reected inside the core, providing that
treatment, featured better insulation performance compared to the beam refraction angle exceeds the critical angle (qc), as
a highly commercial insulating fabric made from polypropylene sketched out in Fig. 25a. When the light is totally conned to
bres, adequate to coat the passenger compartment of trans- the waveguide region, the optical bres are the blueprint
port vehicles. This study of Si and colleagues160 was carried out adequate to the communication eld,266 but such a design
with aerogel composites of 5 mm thickness and an areal density hinders their application in other sensing mechanisms. On the
of 48 g m2; the commercial insulating material was twice other hand, if the light would be able to surpass the boundaries
thicker, with an areal density of 210 g m2. of the travelling area, even in a small portion, it could interact
Motahari and colleagues169 used a cotton bre nonwoven with the surrounding environment, for example, by means of
mat (with an areal density of 800 g m2 and 1 cm thickness) as scattering, absorption or uorescence.268,270 This is the case of
the support matrix to synthesise in situ silica aerogels, and evanescent eld sensing performed by tapered bres, or
assessed the inuence of the molar ratio of MeOH/TEOS and tapers,270 of which an example is draed in Fig. 25b. This type of
ageing time on the composites' sound absorption. The mass of optical bre is used as a sensor of temperature, external
the aerogel in the samples was around 45%. The performance of refractive index,271,272 optical properties of materials,270 in
a composite with a density of 88 kg m3 (molar ratio of 11 and extended environmental monitoring268,272 or clinical
aged for 24 h) was signicantly better than that of the original diagnosis.268
brous matting (more than 1-fold, on average), mainly at Tapered bres are optical bres stretched over a dened
frequencies below 2000 Hz.169 length into thinner diameters, as displayed in Fig. 25b, in which
Feng and co-workers23 manufactured silica aerogel compos- the sensing mechanism occurs though the so-called evanescent
ites (1 cm thickness) with cellulose bres recycled from paper eld: around the bre's waist, an oscillating eld of released
waste. The best performance in sound attenuation was achieved energy is generated, remaining spatially concentrated in the
at 2 wt% bre concentration and 146 kg m3 density. According vicinity of the source.266
to the authors, the coefficient of sound absorption reached 0.5, Aer the high temperature stretching processes to narrow
a higher value compared to that of the commercial polystyrene the waveguide of glass bres, the inherent fragility of those
foams. Moreover, researchers claimed that the cellulose–silica materials is further increased, as the radial dimensions can be
composites have the potential to be scaled up for industrial diminished from 125 mm to a few hundreds of nanometres.266
dimensions, with the interest in them relying on cost- The evanescent region can be as thin as less than 1 mm, and
effectiveness and higher degrees of exibility. therefore is quite prone to contamination or to be damaged.270
In a practical way, silica aerogels embedded with bres can Therefore, a suitable shield is necessary in order to protect the
be tailored to be used as efficient sound barriers with reduced sensing properties of the evanescent eld, for example, from the
thickness compared to the commonly applied materials, such inuence of dust or environment water.266,270 Silica aerogels
as rock wool panels or polystyrene foam, broadening the provide the ideal protection: their high porosity and absorptive
applicability of aerogels where the space for insulation is properties, combined with hydrophobic functionalization, are
limited.23,265 the sought features. Moreover, a hydrophobic aerogel can be
used in the evanescent eld for detection of dissolved gases in
water.266 But the more important related property is the low
4.4 Sensors
refractive index of silica aerogels, and hence they do not inter-
The low refractive index of silica aerogels can be harnessed for fere signicantly with light emissions in the evanescent
the development of sensing devices, for example, to be used in eld.266,273
waveguides and for supporting the performance of optical Additionally to the embedment of optical bres in aero-
bres.266 Due to the total reection phenomenon, a light beam gels,266,273 either by sol–gel coating270 or by laying the bres on
can travel long distances within optical bres, which are known aerogel's surface,274 another version of the applicability of aer-
as well for their immunity against electronic interference and ogels in this technical eld is by lling their hollow-core with
ionizing radiation, large bandwidth, signal accuracy and for the sol, allowing in situ aerogel synthesis.266 Despite the unusual
being light weight and exible.267–269 manufacture of such silica aerogel composites, according to
Grogan266 this conception of waveguide allows broader tailoring
of the optical sensor properties, such as the control of the ow
of light.
The earlier mentioned polyacrylonitrile–silica aerogel
composites, developed by Si and co-workers,160 revealed
elasticity-responsive electrical conduction. The electrically
conductive carbon bres were obtained aer carbonization of
Fig. 25 Optical fibres: (a) total internal reflection within the fibres due
composites, by using the polyacrylonitrile electrospun nano-
to the difference of refractive index between the core and cladding; (b) bres as the precursor for the graphitised carbon, with the
tapered fibre and the evanescent field. electrical conductivity value reported as 0.25 S cm1. The
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exible composite was connected to a ash light-emitting diode important neither to compromise the functional performance
in a 3 V circuit; when subjecting the composites to a stress load of the protective apparel nor hamper the action of users.5 Two
up to 50% of compressive strain, the normalized electrical examples are presented below.
resistance decreased by 70%. The researchers attributed this A cold-water diving suit with incorporated aerogel exhibited
decrease in electric resistance to temporary contact established z76% improved thermal insulation, compared to a market
between bres during compression, adding new electrical standard material with a similar thickness, generally used for
conduction paths. In spite of the broad availability of pressure cold weather clothing (a micro-brous polypropylene batting).
sensors, silica aerogel composites may also have a role in this During the same study, another comparison was made with
application, as described here. neoprene foam, which is generally used in wetsuits, revealing
Chemiresistor gas/vapour sensors were prepared by Boday a 5-fold improvement for the silica aerogel composite. The
and co-workers,68 by imparting electrical conductivity to a silica solution developed by Aspen Aerogels consists in the embedment
aerogel through the addition of polyaniline nanobres. The of the aerogel in a nonwoven fabric in the inner layer of the
work aimed at the application of these silica aerogel composites diving suit, providing a thermal resistance of 12 to 14 clo(†),
in the detection of acidic (HCl) and basic (NH3) gaseous mole- depending on the measurement under different pressure
cules in the environment. The time response accomplished by conditions. Additionally, the thermal performance of this
composites with 9.6 wt% polyaniline nanobres was similar to aerogel-based garment did not exhibit a signicant loss with
that of thin sensor lms cast on electrodes, in which the a so laundering maintenance.275
concentration of polyaniline needed to be signicantly higher The extreme weather conditions experienced by mountain
(several orders of magnitude). Moreover, while the time climbers were also assessed with an Aspen Aerogels product,
response of thin lms decreased with thickness, the perfor- known as Pyrogel®. As stated by Ananthan et al.,5 aer three
mance of polyaniline–silica aerogels was independent of the Mont Blanc routes, two climbers reported the unexpected no
layer thickness, allowing this way thicker materials, hence cold sensation, at severe temperatures of 20 to 25 C and
easier handling of detection materials. The researchers a wind speed of 70–80 km h1.
hypothesized that the speed of response and sensitivity of the Other studies aimed at better protection of re ghters
polyaniline nanober–silica aerogel composites could be during their exigent duties. Aerogel blankets, with applicability
attributed to more open mesoporosity and increased surface in re ghters’ protective clothing, were developed by formation
areas, around two orders of magnitude higher than those of the of a silica network within a meta-aramid brous batting. The
lm of polyaniline bers. Boday et al.68 also mentioned that composites, dried at ambient pressure, were subjected to sily-
polyaniline–silica aerogel composites, with 16.5 wt% polyani- lation treatment with TMCS, imparting hydrophobicity,
line nanobres, displayed higher electrical conductivity values decreased density and consequently better results in thermal
than a polyvinyl alcohol aerogel loaded with 12 mg L1 of insulation. Aer a comparative evaluation with conventional
carbon nanotubes. non-aerogel blankets, the silica aerogel blankets revealed an
increased protection of 58% regarding burn injury hazard.33
Aerogel based materials prevent heat ux, which is advan-
4.5 Technical and protective apparel tageous for inhibiting the incoming heat, but may hinder the
The concept of conventional insulation clothing is based on airy necessary heat exchange balance of the human body.276,277 Shaid
textile structures (non-woven fabrics), exible foams (poly- and co-workers278 evaluated the heat stress of re ghters, when
urethane layers) or bres with a hollow core. Higher thermal the body temperature rises beyond the safe limits. In their
insulation performance requires higher thickness (successive approach, they combined the use of aerogel particles along with
layers of fabric or foam), which might restrain the user's phase change materials (PCMs). PCMs have the ability to store
movements.139 and release heat according to the changing environment
Aerogels are indeed a major breakthrough when applied to temperature. A mixture of a dispersion of nanoporous aerogel
apparel, due to their proved efficiency at reduced thickness. particles, melted eicosane (an organic PCM with a phase tran-
Fabrics with integrated aerogels can provide up to six times sition temperature around 37 C) and a coating textile binder
more insulation performance, with the same fabric thickness, was applied to the inner layer of the Nomex® fabric(‡), by an
than conventional insulating clothing.139 Aerogel based mate- impregnation process. The aerogel particles and the binder
rials encompass the needed features to be used for protection paste were applied to the outer layer of the Nomex® fabric.
from thermal and electric hazards, to protect workers exposed PCMs absorbed metabolic heat, circumventing the reduction of
to molten substances or from ames or radiant heat.33 heat exchange that results from the almost null permeability of
Aspen Aerogels Inc. led the manufacturing of aerogel blan-
kets, whose industrial production started around 2003,80 with
the insulation products resembling textile-like materials.123 The † Clothing insulation can be expressed in clo units. 1 clo is the thermal resistance
production techniques involve alkoxysilane precursors and CO2 assigned as 0.155 m2 K W1, where 1 clo represents the insulation of a suit
provided to a resting man to maintain the comfort at 21.1 C, with a relative
supercritical drying,83 with the product being around 10 times
humidity of less than 50% and an air velocity of 0.102 m s1.309
more expensive than conventional materials with the same level ‡ Nomex® is the commercial brand of an aramid bre with meta-oriented
of insulation.132 Notwithstanding, when it comes to people linkages, stable at a temperature as high as 500 C for small periods of time;
operating in an extreme temperature environment, it is quite for long term exposure, it can withstand until 220 C.185
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the aerogel treated fabric. According to the authors, the aerogel/ as the silica precursor. Both networks remained closely
PCM mixture proved to be efficient for re ghters’ equipment, adhered, surrounded by each other without additional chemical
since the time until the pain threshold (when the human body bonds. Flexible composites were developed, encompassing
temperature rises up to 44 C) was delayed by more than 2- super-hydrophobicity (165 ), low density (123 kg m3) and low
fold.278 The advantages of silica aerogel porosity for the inl- thermal conductivity (z45 mW m1 K1).
tration of melt PCMs for textile thermoregulatory applications Cellulose derived scaffolds, oen involving the freeze-drying
are thoroughly detailed in other studies.279,280 technique in their manufacture,46,241,290 are also being used as
Another benet of the aerogel-based fabrics is their relatively silica aerogel reinforcement frameworks. The broad availability
reduced thickness, hence less bulky aesthetic appearance, of a renewable source might suggest a more sustainable
which allows adding design to protective clothing, for example, approach of the concept, but among the current drying tech-
in ski suits.139 nologies, freeze-drying is considered too expensive due to its
inefficiency in energy consumption.291 Nonetheless, in the
4.6 Other applications scientic research domain, good results can be found for silica
aerogels reinforced with cellulose templates, both in terms of
According to several authors,16,153,281–283 silica aerogels rein- robustness and thermal insulation (in spite of the unmodied
forced with ceramic quartz bre felt can provide a structural freeze-dried nanobrous scaffolds typically encompassing high
frame for the encapsulation of enzymes, allowing their use for values of thermal conductivity292). Zhao and co-workers241
repeated cycles.153,281 Enzymes were added to the silica sol developed a silylated framework, by adding MTMS to an
before gelation and the gel was supercritically dried with CO2. aqueous suspension of nanobrillated cellulose (with such
The aerogel encapsulation technique potentiates a homoge- a modication, the authors intended as well to further improve
neous dispersion of enzymes,16 enabling higher concentrations, the adhesion between the scaffold and the aerogel particles);
as well as the enhancement of the catalytic activity per mass of aer that, the silica sol at the onset of gelation was cast into
enzyme.153 The enzymes studied were lipases, used for the a mould containing the previously prepared scaffold. Addi-
esterication of lauric acid with 1-octanol,153,281 trans- tionally, the gels were subjected to a hydrophobic treatment
esterication of sunower seed oil with methyl acetate16 and with HMDZ and supercritically dried. The composites displayed
methanol,282 and partial transesterication of sunower oil with super-insulating properties (less than 20 mW m1 K1), and the
ethanol.283 compressive modulus increased by 55% and maximum tensile
Karout and co-workers153 also tried to use carbon bre felt in strength increased by 126%, compared to the 100% silica aer-
this context, which they claimed to provide extra reinforcement ogel reference sample.241
to silica aerogels. In terms of catalytic activity, the results were Other researchers were inspired by nature, by mimicking
as good as those obtained by enzyme encapsulation in aerogels birds' nests.243,293 Birds developed the expeditious technique of
reinforced with ceramic bre felt. However, the authors re- lling the tree branch structures with highly insulating mate-
ported that hydrophobic carbon felt performed better with rials, such as feathers or animal wool, decreasing the lap-
silica precursors with high ratio of hydrophobic groups, while branch holes to below the mean free path of air. The aerogel
ceramic felt should be preferentially used to strengthen aero- mimic was achieved with mullite bres, as the macrostructure,
gels synthesised with low proportion of hydrophobic groups.153 and silica–boron293 or silica–zirconia243 sols to ll the inter-
Other applications of silica aerogels reinforced with bres stices. High performance materials were then synthesised, able
are mentioned in the literature as ltering media,13,160 corrosion to endure load stress and extreme temperatures. For example,
resistant insulators,284 separators of electric charged mate- in terms of compressive strength, an increase up to 1.05 MPa
rials,160,285 shock absorbers286 or even tissue engineering was reported, around ten-fold compared to the reference pris-
scaffolds.160,287 tine aerogel;243 or improved exibility, with the limit of elastic
Also, the non-toxic nature of silica aerogels and sufficient region dened at 2.2 MPa (more than two fold in comparison
biocompatibility with mammals allow them to be used in the with silica aerogels), and rebound resilience at 2.0 MPa, still
pharmaceutical industry, for example as supports of controlled performing at z86%, even when subjected to an environment
drug delivery.287–289 of 1000 C.293 Moreover, it has been recently accepted that
ceramic nanocrystalline nanobres combine the high aspect
5 New trends and future perspectives ratio with a nanometer-sized grain, encompassing the needed
exibility to be used for 3D elastic assemblies.190
Apart from the well-established method of bre embedment, Aer this exhaustive literature survey, there is absolutely no
another emerging way to develop exible and reinforced aerogel doubt over the huge potential of silica aerogels, mainly for
composites is through the scaffold concept. It consists of a two- insulation purposes.294 According to Koebel et al.,140 “buildings
step manufacturing process, starting with the assembly of are a tremendous market opportunity”, since transport enter-
a macro-porous solid template (either a rigid or exible struc- prises have been investing in energy efficient systems, mainly
ture), which in turn will be dipped in the silica sol that for economic motivations. Now, as the climate change protocols
undergoes gelation, lling with a nanostructured matrix the demand for diminished CO2 emissions295 along with EU
macropores of the template. As an example, Mahadik et al.284 Directives on building energy efficiency,296 heating, ventilation
used 2-ethylhexyl acrylate for the scaffold synthesis, and MTMS and air conditioning of buildings remain as the tackling
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issues,140 and so insulating materials with improved efficiency However, further research is needed to fully assess the effect of
are effervescently sought.284,297 the presence of bres during gelation and correlate the porous
Vacuum insulation panels (VIPs)140,298,299 and aerogels140,294,298 nanostructure features with the type/properties of bres and the
were accepted as being the cutting edge technology in this context, possible chemical interaction between the two phases. This can
whose typical values of thermal conductivity are around 4 and 13 be performed by using high-resolution microscopy techniques
mW m1 K1, respectively. Both materials are very expensive, but and molecular modelling studies. In fact, the outstanding
VIPs seem to be more cost-effective,298 with their use being sug- thermal insulation performance of silica aerogels relies on their
gested in the retrot of public historic buildings (even if it was nanoporous structure. Thus, any change of the silica network
with some restrictions).299 However, the thermal conductivity of that causes the enlargement of pores may have a detrimental
VIPs tends to deteriorate with ageing, due to moisture and air effect on the insulation performance of aerogels, and must be
penetration by diffusion,140,298 while aerogels can be made hydro- prevented. Their high thermal efficiency at reduced thickness
phobic, with no loss of performance due to ageing.298 makes them appropriate in cases of space limitation, as can be
Currently, the aerogel market provides high value-added the case of retrotting of important old building facades,305,306
products, in areas that justify their cost,298 mainly in the form where the requirements of historical preservation include the
of aerogel blankets, as mentioned above (Section 3.1). maintenance of their appearance.
It is predicted that, in near future, the decreased costs of The production of large-scale silica aerogel monolithic
aerogels will propel their use as the main insulation resource; in shapes can be better accomplished with extra reinforcement, by
2008, the cost of an aerogel was z£ 3000 m3, and it is esti- following the composite approach, involving the embedment of
mated that, by 2050, its price will fall below £500 m3.300 brous materials, mainly in the matt form, but also aer bre
Several strategies have been already implemented to improve dispersion in the initial sol.83,307 Besides the already imple-
aerogels’ cost-effectiveness: mented industrial processes (for example, Aspen Inc., Cabot
(1) Cost-effective precursors, as is the case of sodium sili- Corporation, and Nano High-Tech Co., Ltd), novel methodologies
cate,4,46 or those retrieved from agro-industrial wastes, such as are being researched at the laboratory domain to scale-up aer-
rice hull ash;4 ogel manufacture.115,241,308
(2) Diversication of aerogel reinforcement materials, taking As already exposed, aerogel syntheses have numerous
into account their availability and footprint,162 favouring those constraints and are difficult to control, which oen cause the lack
obtained from wastes23,83 or other industrial by-products;159 of a standardised product.294 But there are promising scenarios:
(3) Simplied processes that decrease the manufacturing a patented process of the French company SEPAREX S.A.,
time and reduce wastes;41,46,301 involving SCD, allows greater uniformity of the internal structure
(4) APD;40,300 and better results in terms of thermal conductivity.294 Another
(5) For specic needs only accomplished with SCD, the CO2 solution may be the evacuation and sealing of silica aerogels,
uid might be a sustainable option.89,302 This is not, however, which can reduce their thermal conductivity by 50%,139 a possible
a consensual conclusion. According to a life cycle assessment way of circumventing the loss of insulation performance due to
(on the laboratory scale) for silica aerogels synthesized under bre addition, considering the composite approach.
high and low temperature SCD, the greater environmental The traditional insulation materials, either in the form of
burdens (both in energy consumption and in CO2 emissions) mineral bre panels or polymeric foams, currently account for
were due to the CO2 SCD aerogels.303 the largest market shares, due to their relatively accessible costs
A recent successful case of aerogel technology transfer from the and high moisture resistance.23 In line with an European report
laboratory to market, due to a cost reduction of z70% (although on aerogels,294 the focus of public-funded research should be
in a granular form; brand-named Quartzene®), is a material syn- geared towards increasing the market attractiveness, capital-
thesised with affordable precursors and APD. Also, according to ising on aerogels’ unique features. As referred by Fricke258
the authors, their manufacture is environmentally friendly.304 (going back to 1992), there is a need for effective environmen-
tally friendly, non-hazardous, non-inammable thermal insu-
lation materials to replace polymeric foams. The frenetic
5.1 Final considerations scientic research in silica aerogels with embedded bres is in
Aerogels are viewed as a new class of materials in terms of their pursuit of those goals.
chemical architecture,58 being some of the most promising Also, the successful development of such auspicious mate-
nanomaterials for effective insulation barriers, also taking rials may provide unexpected insights for new advanced appli-
advantage of non-ammable properties of silica.265 However, cations, for example, as novel drug carriers, either for
aerogels' inherent friability derived from the porous structure, agriculture or health applications, tackling the two most
and current prohibitive manufacturing costs, impairs their up- important sectors of growing worldwide population.
take by the market.115,294
Fibre embedment in silica aerogels imparts additional Disclaimer
strength to the composites, while acting as starting spots for the
development of colloidal networks during the gelation event.68 The mention to enterprises or market products does not stand
Thus, bres tend to act as nucleation agents,68 diminishing for recommendation or endorsement by the authors nor by the
manufacturing time and ultimately the price of aerogels. Royal Society of Chemistry.
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Conflicts of interest 16 O. Orçaire, P. Buisson and A. C. Pierre, J. Mol. Catal. B:

Enzym., 2006, 42, 106–113.
There are no conicts to declare. 17 C. C. Li, Y. T. Chen, Y. T. Lin, S. F. Sie and Y. W. Chen-Yang,
Colloids Surf., B, 2014, 115, 191–196.
Acknowledgements 18 P. C. Thapliyal and K. Singh, J. Mater., 2014, 2014, 10.
19 M. F. Mora, S. M. Jones, J. Creamer and P. A. Willis,
The authors acknowledge Professors Maria Helena Gil, António Electrophoresis, 2018, 39, 620–625.
Portugal and Jorge Coelho for their support in the improvement 20 Z. Qi, D. Huang, S. He, H. Yang, Y. Hu, L. Li and H. Zhang, J.
of the text. Funding: this work was funded by Fundação para Eng. Fibers Fabr., 2013, 8, 134–139.
a Ciência e Tecnologia, I.P., through a doctoral degree grant 21 I. Michaeloudis, Can we put the sky into a bottle?, https://
[SFRH/BD/131819/2017]; this work was also supported by the www.youtube.com/watch?v¼prWpMLB_2Xw.
European Regional Development Fund (ERDF), through 22 Method for production of exible panels of hydrophobic
COMPETE 2020 – Operational Programme for Competitiveness aerogel reinforced with bre felts, WO2015016730A2,
and Internationalization, combined with Portuguese National 2015, 1–7.
Funds, through Fundação para a Ciência e Tecnologia, I.P. 23 J. Feng, D. Le, S. T. Nguyen, V. Tan Chin Nien, D. Jewell and
[POCI-01-0145-FEDER-006910 (UID/EQU/00102/2013); POCI-01- H. M. Duong, Colloids Surf., A, 2016, 506, 298–305.
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Silica Aerogel Composites With Embedded Fibres

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Silica Aerogel Composites With Embedded Fibres

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Silica aerogel composites with embedded ﬁbres:

Cite this: J. Mater. Chem. A, 2019, 7,

drawbacks, such as dust release,22,34,35 hydrophilicity,9,33,35 volu-

Review Journal of Materials Chemistry A

formed from solution by a progressive change of liquid

tends to crush, as the chains impinge on one another due to

Table 1 Typical properties (range of values) of silica aerogels

Property Units Range values References

Journal of Materials Chemistry A Review

crack due to the unbalanced forces.75,81

Review Journal of Materials Chemistry A

has a signicant impact on the reaction kinetics, leading to the

17.5 (at z20 C)

14.1 (at z20 C)

with low specic surface area.93,95

liquid-phase meniscus stresses. By a fast freezing of the solvent,

applied to drying hydrogels,96 since the solidication of water is

more readily accessible than for usual organic solvents.

The lyophilisation cycle encompasses three steps: (a)

lowering the temperature of the solvent (inside the pores) below

process is prone to the formation of microcrystalline salt-like

a result, pore size tends to be augmented, compared to the case

Clay based aerogels are generally dried by freeze-drying. It is

generally accepted that, during the drying process, a rearrange-

aerogels.97,98 This kind of material fullls the needed features of

ame retardant materials.99–101

2.3.3 Ambient pressure drying. The simple evaporation at

ambient pressure seems to be the most obvious method to

remove the solvent from a porous material, by raising the

temperature above the solvent’s boiling point and turning it

into a gas – this is the basic principle of APD.80

The solvent within the system coexists in three states: the

nanopores, and cause cracks in the structure.80 Oen there is

drying surpass the elastic limit of the solid structure, generating

granular aerogels.43,83 This is particularly signicant with pore

mats or blankets).80 The volume of the xerogel is reduced by

a factor of 5–10, compared to the dimensions of the gel.102

2.4 Strategies to minimize APD shrinkage

APD is an advantageous drying technique when taking into

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

are responsible for the interaction with silica.175 In addition, Li

bres were encircled by aerogel fragments (Fig. 7b), revealing

22776 | J. Mater. Chem. A, 2019, 7, 22768–22802

This journal is © The Royal Society of Chemistry 2019

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

of cellulose bres, combined with APD drying, enable a facile

Thermal conductivity (mW

This journal is © The Royal Society of Chemistry 2019

Journal of Materials Chemistry A

J. Mater. Chem. A, 2019, 7, 22768–22802 | 22779

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Fig. 10 Silica aerogels’ (a) cumulative volume shrinkage (during ageing

trimethylchlorosilane (TMCS/ethanol/n-hexane solution),

Journal of Materials Chemistry A Review

mance of a polyaniline–silica composite aerogel was 200%

Review Journal of Materials Chemistry A

3.6 Eﬀect of bre content on the thermal conductivity of

Journal of Materials Chemistry A Review